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COMPREHENSIVE
ORGANOMETALLIC
CHEMISTRY IV
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COMPREHENSIVE
ORGANOMETALLIC
CHEMISTRY IV
EDITORS-IN-CHIEF
GERARD PARKIN
Department of Chemistry, Columbia University, New York, NY, United States
KARSTEN MEYER
Department of Chemistry and Pharmacy, Friedrich-Alexander-Universität, Erlangen, Germany
DERMOT O’HARE
Department of Chemistry, University of Oxford, Oxford, United Kingdom
VOLUME 1
FUNDAMENTALS
VOLUME EDITOR
PATRICK L. HOLLAND
Yale University, New Haven, United States
Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including
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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted
herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in
research methods, professional practices, or medical treatment may become necessary.
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To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or
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products, instructions, or ideas contained in the material herein.
Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library
ISBN 978-0-12-820206-7
For information on all publications visit our

website at http://store.elsevier.com
Publisher: Oliver Walter

Acquisition Editor: Blerina Osmanaj
Content Project Manager: Claire Byrne
Associate Content Project Manager: Fahmida Sultana
Designer: Christian Bilbow
CONTENTS OF VOLUME 1
Editor Biographies vii

Contributors to Volume 1 xiii
Preface xv
1.01 Introduction: Volume I 1

Patrick L Holland
1.02 Models for Understanding Main Group and Transition Metal Bonding 2
Aaron L Odom
1.03 Reversible Homolysis of Metal-Carbon Bonds 31

Maxime Michelas, Christophe Fliedel, and Rinaldo Poli
1.04 Very Low Oxidation States in Organometallic Chemistry 86

C Gunnar Werncke
1.05 Very High Oxidation States in Organometallic Chemistry 109

Moritz Malischewski
1.06 Characterization Methods for Paramagnetic Organometallic Complexes 135

Aleksa Radovic, Shilpa Bhatia, and Michael L Neidig
1.07 Computational Methods in Organometallic Chemistry 176

S Chantal E Stieber
1.08 f-Element Organometallic Single-Molecule Magnets 211

Richard A Layfield, Christopher GT Price, and Siobhan R Temple
1.09 Electrochemistry in Organometallic Chemistry 249

Julie A Hopkins Leseberg, Wade C Henke, and James D Blakemore
1.10 Organometallic Photosensitizers 284

Thomas S Teets and Yanyu Wu
1.11 Organometallic Chemistry of NHCs and Analogues 339

Liang Deng and Zhenbo Mo
1.12 Ligands Featuring Covalently Tethered Moderate to Weakly Coordinating Anions 373
Anton W Tomich, Varun Tej, Sergio Lovera, Isaac Banda, Steven Fisher, Matthew Asay, and Vincent Lavallo
1.13 Redox-Active Ligands in Organometallic Chemistry 421

Errikos Kounalis and Daniël LJ Broere
1.14 Proton Responsive and Hydrogen Bonding Ligands in Organometallic Chemistry 442
Elizabeth T Papish, Sanjit Das, Weerachai Silprakob, Chance M Boudreaux, and Sonya Manafe
1.15 Introduction to the Organometallic Chemistry of Carbon Dioxide 474

Charles W Machan
1.16 Alkane s-Complexes 502

Rowan D Young
v
vi Contents of Volume 1
1.17 Dinitrogen Binding and Functionalization 521

Jeremy E Weber, Samuel M Bhutto, Alexandre T-Y Genoux, and Patrick L Holland
1.18 Lewis Acid Participation in Organometallic Chemistry 555

Julia B Curley, Nilay Hazari, and Tanya M Townsend
1.19 Organometallic Chemistry on Oxide Surfaces 583

Matthew P Conley, Jiaxin Gao, Winn Huynh, Jessica Rodriguez, and Kavyasripriya K Samudrala
1.20 Separation Strategies in Organometallic Catalysis 609

Fernanda G Mendonça and R Tom Baker
1.21 Impurities in Organometallic Catalysis 635

Nicholas E Leadbeater
EDITOR BIOGRAPHIES
Editors in Chief
Karsten Meyer studied chemistry at the Ruhr University Bochum and performed
his Ph.D. thesis work on the molecular and electronic structure of first-row
transition metal complexes under the direction of Professor Karl Wieghardt at
the Max Planck Institute in Mülheim/Ruhr (Germany). He then proceeded to
gain research experience in the laboratory of Professor Christopher Cummins at
the Massachusetts Institute of Technology (USA), where he appreciated the art of
synthesis and developed his passion for the coordination chemistry and reactivity
of uranium complexes. In 2001, he was appointed to the University of California,
San Diego, as an assistant professor and was named an Alfred P. Sloan Fellow in
2004. In 2006, he accepted an offer (C4/W3) to be the chair of the Institute of
Inorganic & General Chemistry at the Friedrich-Alexander-University Erlangen-
Nürnberg (FAU), Germany. Among his awards and honors, he was elected a
lifetime honorary member of the Israel Chemical Society and a fellow of the
Royal Society of Chemistry (UK). Karsten received the Elhuyar-Goldschmidt Award from the Royal Society of
Chemistry of Spain, the Ludwig Mond Award from the RSC (UK), and the Chugaev Commemorative Medal
from the Russian Academy of Sciences. He has also enjoyed visiting professorship positions at the universities of
Manchester (UK) and Toulouse (F) as well as the Nagoya Institute of Technology (JP) and ETH Zürich (CH).
The Meyer lab research focuses on the synthesis of custom-tailored ligand environments and their transition
and actinide metal coordination complexes. These complexes often exhibit unprecedented coordination modes,
unusual electronic structures, and, consequently, enhanced reactivities toward small molecules of biological
and industrial importance. Interestingly, Karsten’s favorite molecule is one that exhibits little reactivity: the
Th symmetric U(dbabh)6.
Dermot O’Hare was born in Newry, Co Down. He studied at Balliol College,

Oxford University, where he obtained his B.A., M.A., and D.Phil. degrees under
the direction of Professor M.L.H. Green. In 1985, he was awarded a Royal
Commission of 1851 Research Fellowship, during this Fellowship he was a
visiting research fellow at the DuPont Central Research Department, Wilming-
ton, Delaware in 1986–87 in the group led by Prof. J.S. Miller working on
molecular-based magnetic materials. In 1987 he returned to Oxford to a
short-term university lectureship and in 1990 he was appointed to a permanent
university position and a Septcentenary Tutorial Fellowship at Balliol College.
He has previously been honored by the Institüt de France, Académie des Sciences
as a leading scientist in Europe under 40 years. He is currently professor of
organometallic and materials chemistry in the Department of Chemistry at the
University of Oxford. In addition, he is currently the director of the SCG-Oxford
Centre of Excellence for chemistry and associate head for business & innovation in the Mathematics, Physical
and Life Sciences Division. He leads a multidisciplinary research team that works across broad areas of catalysis
and nanomaterials. His research is specifically targeted at finding solutions to global issues relating to energy,
zero carbon, and the circular economy. He has been awarded numerous awards and prizes for his creative and
vii
viii Editor Biographies
ground-breaking work in inorganic chemistry, including the Royal Society Chemistry’s Sir Edward Frankland
Fellowship, Ludwig Mond Prize, Tilden Medal, and Academia–Industry Prize and the Exxon European Chem-
ical and Engineering Prize.
Gerard Parkin received his B.A., M.A., and D.Phil. degrees from the Queen’s
College, Oxford University, where he carried out research under the guidance of
Professor Malcolm L.H. Green. In 1985, he moved to the California Institute of
Technology as a NATO postdoctoral fellow to work with Professor John
E. Bercaw. He joined the Faculty of Columbia University as assistant professor
in 1988 and was promoted to associate professor in 1991 and to professor in
1994. He served as chairman of the Department from 1999 to 2002. He has also
served as chair of the New York Section of the American Chemical Society, chair
of the Inorganic Chemistry and Catalytic Science Section of the New York Acad-
emy of Sciences, chair of the Organometallic Subdivision of the American Chem-
ical Society Division of Inorganic Chemistry, and chair of the Gordon Research
Conference in Organometallic Chemistry.
He is an elected fellow of the American Chemical Society, the Royal Society of
Chemistry, and the American Association for the Advancement of Science, and is the recipient of a variety of
international awards, including the ACS Award in pure chemistry, the ACS Award in organometallic chemistry,
the RSC Corday Morgan Medal, the RSC Award in organometallic chemistry, the RSC Ludwig Mond Award, and
the RSC Chem Soc Rev Lecture Award. He is also the recipient of the United States Presidential Award for
Excellence in Science, Mathematics and Engineering Mentoring, the United States Presidential Faculty Fellow-
ship Award, the James Flack Norris Award for Outstanding Achievement in the Teaching of Chemistry, the
Columbia University Presidential Award for Outstanding Teaching, and the Lenfest Distinguished Columbia
Faculty Award.
His principal research interests are in the areas of synthetic, structural, and mechanistic inorganic chemistry.
Volume Editors
Simon Aldridge is professor of chemistry at the University of Oxford and

director of the UKRI Centre for Doctoral Training in inorganic chemistry for
Future Manufacturing. Originally from Shrewsbury, England, he received both
his B.A. and D.Phil. degrees from the University of Oxford, the latter in 1996 for
work on hydride chemistry under the supervision of Tony Downs. After
post-doctoral work as a Fulbright Scholar at Notre Dame with Tom Fehlner,
and at Imperial College London (with Mike Mingos), he took up his first aca-
demic position at Cardiff University in 1998. He returned to Oxford in 2007,
being promoted to full professor in 2010. Prof. Aldridge has published more than
230 papers to date and is a past winner of the Dalton Transactions European
Lectureship (2009), the Royal Society of Chemistry’s Main Group Chemistry
(2010) and Frankland Awards (2018), and the Forschungspreis of the Alexander
von Humboldt Foundation (2021). Prof. Aldridge’s research interests are primar-
ily focused on main group organometallic chemistry, and in particular the development of compounds with
unusual electronic structure, and their applications in small molecule activation and catalysis (website: http://
aldridge.web.ox.ac.uk).
(Picture credit: John Cairns)
Editor Biographies ix
Eszter Boros is associate professor of chemistry at Stony Brook University with

courtesy appointments in radiology and pharmacology at Stony Brook Medicine.
Eszter obtained her M.Sc. (2007) at the University of Zurich, Switzerland and her
Ph.D. (2011) in chemistry from the University of British Columbia, Canada. She
was a postdoc (2011–15) and later instructor (2015–17) in radiology at Massa-
chusetts General Hospital and Harvard Medical School. In 2017, Eszter was
appointed as assistant professor of chemistry at Stony Brook University, where
her research group develops new approaches to metal-based diagnostics and
therapeutics at the interfaces of radiochemistry, inorganic chemistry and medi-
cine. Her lab’s work has been extensively recognized; Eszter holds various major
federal grants (NSF CAREER Award, NIH NIBIB R21 Trailblazer, NIH NIGMS
R35 MIRA) and has been named a 2020 Moore Inventor Fellow, the 2020
Jonathan L. Sessler Fellow (American Chemical Society, Inorganic Division),
recipient of a 2021 ACS Infectious Diseases/ACS Division of Biological Chemistry Young Investigator Award
(American Chemical Society), and was also named a 2022 Alfred P. Sloan Research Fellow in chemistry.
Scott R. Daly is associate professor of chemistry at the University of Iowa in

the United States. After spending 3 years in the U.S. Army, he obtained his B.S.
degree in chemistry in 2006 from North Central College, a small liberal arts
college in Naperville, Illinois. He then went on to receive his Ph.D. at the
University of Illinois at Urbana-Champaign in 2010 under the guidance of
Professor Gregory S. Girolami. His thesis research focused on the synthesis and
characterization of chelating borohydride ligands and their use in the preparation
of volatile metal complexes for chemical vapor deposition applications. In 2010,
he began working as a Seaborg postdoctoral fellow with Drs. Stosh A. Kozimor
and David L. Clark at Los Alamos National Laboratory in Los Alamos, New
Mexico. His research there concentrated on the development of ligand K-edge
X-ray absorption spectroscopy (XAS) to investigate covalent metal–ligand bond-
ing and electronic structure variations in actinide, lanthanide, and transition
metal complexes with metal extractants. He started his independent career in 2012 at George Washington
University in Washington, DC, and moved to the University of Iowa shortly thereafter in 2014.
His current research interests focus on synthetic coordination chemistry and ligand design with emphasis on
the development of chemical and redox noninnocent ligands, mechanochemical synthesis and separation
methods, and ligand K-edge XAS. His research and outreach efforts have been recognized with an Outstanding
Faculty/Staff Advocate Award from the University of Iowa Veterans Association (2016), a National Science
Foundation CAREER Award (2017), and a Hawkeye Distinguished Veterans Award (2018). He was promoted to
associate professor with distinction as a College of Liberal Arts and Sciences Deans Scholar in 2020.
Lena J. Daumann is currently professor of bioinorganic and coordination

chemistry at the Ludwig Maximilian Universität in Munich. She studied chemistry
at the University of Heidelberg working with Prof. Peter Comba and subsequently
conducted her Ph.D. at the University of Queensland (Australia) from 2010 to
2013 holding IPRS and UQ Centennial fellowships. In 2013 she was part of the
Australian Delegation for the 63rd Lindau Nobel Laureate meeting in chemistry.
Following postdoctoral stays at UC Berkeley with Prof. Ken Raymond (2013–15)
and in Heidelberg, funded by the Alexander von Humboldt Foundation, she
started her independent career at the LMU Munich in 2016. Her bioinorganic
research group works on elucidating the role of lanthanides for bacteria as well as
on iron enzymes and small biomimetic complexes that play a role in epigenetics
and DNA repair. Daumann’s teaching and research have been recognized with
numerous awards and grants. Among them are the national Ars Legendi Prize for
chemistry and the Therese von Bayern Prize in 2019 and the Dozentenpreis of the “Fonds der Chemischen
Industrie“ in 2021. In 2018 she was selected as fellow for the Klaus Tschira Boost Fund by the German Scholars
Organisation and in 2020 she received a Starting grant of the European Research Council to study the uptake of
lanthanides by bacteria.
x Editor Biographies
Derek P. Gates hails from Halifax, Nova Scotia (Canada) where he completed
his B.Sc. (Honours Chemistry) degree at Dalhousie University in 1993.
He completed his Ph.D. degree under the supervision of Professor Ian Manners
at the University of Toronto in 1997. He then joined the group of Professor
Maurice Brookhart as an NSERC postdoctoral fellow at the University of North
Carolina at Chapel Hill (USA). He began his independent research career in 1999
as an assistant professor at the University of British Columbia in Vancouver
(Canada). He has been promoted through the ranks and has held the position
of professor of chemistry since 2011. At UBC, he has received the Science Under-
graduate Society—Teaching Excellence Award, the Canadian National Commit-
tee for IUPAC Award, and the Chemical Society of Canada—Strem Chemicals
Award for pure or applied inorganic chemistry. His research interests bridge the
traditional fields of inorganic and polymer chemistry with particular focus on
phosphorus chemistry. Key topics include the discovery of novel structures, unusual bonding, new reactivity,
along with applications in catalysis and materials science.
Patrick Holland performed his Ph.D. research in organometallic chemistry at UC

Berkeley with Richard Andersen and Robert Bergman. He then learned about
bioinorganic chemistry through postdoctoral research on copper-O2 and
copper-thiolate chemistry with William Tolman at the University of Minnesota.
His independent research at the University of Rochester initially focused on
systematic development of the properties and reactions of three-coordinate
complexes of iron and cobalt, which can engage in a range of bond activation
reactions and organometallic transformations. Since then, his research group has
broadened its studies to iron-N2 chemistry, reactive metal–ligand multiple
bonds, iron–sulfur clusters, engineered metalloproteins, redox-active ligands,
and solar fuel production. In 2013, Prof. Holland moved to Yale University,
where he is now Conkey P. Whitehead Professor of Chemistry. His research has
been recognized with an NSF CAREER Award, a Sloan Research Award, Fulbright
and Humboldt Fellowships, a Blavatnik Award for Young Scientists, and was elected as fellow of the American
Association for the Advancement of Science. In the area of N2 reduction, his group has established molecular
principles to weaken and break the strong N–N bond, in order to use this abundant resource for energy and
synthesis. His group has made a particular effort to gain an insight into iron chemistry relevant to nitrogenase,
the enzyme that reduces N2 in nature. His group also maintains an active program in the use of inexpensive
metals for transformations of alkenes. Mechanistic details are a central motivation to Prof. Holland and the
wonderful group of over 80 students with whom he has worked.
Steve Liddle was born in Sunderland in the North East of England and gained
his B.Sc. (Hons) and Ph.D. from Newcastle University. After postdoctoral fellow-
ships at Edinburgh, Newcastle, and Nottingham Universities he began his inde-
pendent career at Nottingham University in 2007 with a Royal Society University
Research Fellowship. This was held in conjunction with a proleptic Lectureship
and he was promoted through the ranks to associate professor and reader in 2010
and professor of inorganic chemistry in 2013. He remained at Nottingham until
2015 when he was appointed professor and head of inorganic chemistry and
co-director of the Centre for Radiochemistry Research at The University of Man-
chester. He has been a recipient of an EPSRC Established Career Fellowship and
ERC Starter and Consolidator grants. He is an elected fellow of The Royal Society
of Edinburgh and fellow of the Royal Society of Chemistry and he is vice
president to the Executive Committee of the European Rare Earth and Actinide
Society. His principal research interests are focused on f-element chemistry, involving exploratory synthetic
chemistry coupled to detailed electronic structure and reactivity studies to elucidate structure-bonding-property
relationships. He is the recipient of a variety of prizes, including the IChemE Petronas Team Award for
Excellence in Education and Training, the RSC Sir Edward Frankland Fellowship, the RSC Radiochemistry
Editor Biographies xi
Group Bill Newton Award, a 41st ICCC Rising Star Award, the RSC Corday-Morgan Prize, an Alexander von
Humboldt Foundation Friedrich Wilhelm Bessel Research Award, the RSC Tilden Prize, and an RSC Dalton
Division Horizon Team Prize. He has published over 220 research articles, reviews, and book chapters to date.
David Liptrot received his MChem (Hons) in chemistry with Industrial Train-
ing from the University of Bath in 2011 and remained there to undertake a Ph.D.
on group 2 catalysis in the laboratory of Professor Mike Hill. After completing this
in 2015 he took up a Lindemann Postdoctoral Fellowship with Professor Philip
Power FRS (University of California, Davis, USA). In 2017 he began his indepen-
dent career returning to the University of Bath and in 2019 was awarded a Royal
Society University Research Fellowship. His interests concern new synthetic
methodologies to introduce main group elements into functional molecules
and materials.
David P. Mills hails from Llanbradach and Caerphilly in the South Wales
Valleys. He completed his MChem (2004) and Ph.D. (2008) degrees at Cardiff
University, with his doctorate in low oxidation state gallium chemistry super-
vised by Professor Cameron Jones. He moved to the University of Nottingham
in 2008 to work with Professor Stephen Liddle for postdoctoral studies in
lanthanide and actinide methanediide chemistry. In 2012 he moved to the
University of Manchester to start his independent career as a lecturer, where he
has since been promoted to full professor of inorganic chemistry in 2021.
Although he is interested in all aspects of nonaqueous synthetic chemistry his
research interests are currently focused on the synthesis and characterization of
f-block complexes with unusual geometries and bonding regimes, with the aim
of enhancing physicochemical properties. He has been recognized for his con-
tributions to both research and teaching with prizes and awards, including a
Harrison-Meldola Memorial Prize (2018), the Radiochemistry Group Bill Newton Award (2019), and a Team
Member of the Molecular Magnetism Group for the Dalton Division Horizon Prize (2021) from the Royal
Society of Chemistry. He was a Blavatnik Awards for Young Scientists in the United Kingdom Finalist in
Chemistry in 2021 and he currently holds a European Research Council Consolidator Grant.
Ian Tonks is the Lloyd H. Reyerson professor at the University of Minneso-

taTwin Cities, and associate editor for the ACS journal Organometallics.
He received his B.A. in chemistry from Columbia University in 2006 and per-
formed undergraduate research with Prof. Ged Parkin. He earned his Ph.D. in
2012 from the California Institute of Technology, where he worked with Prof.
John Bercaw on olefin polymerization catalysis and early transition metal-ligand
multiply bonded complexes. After postdoctoral research with Prof. Clark Landis
at the University of Wisconsin, Madison, he began his independent career at the
University of Minnesota in 2013 and earned tenure in 2019. His current research
interests are focused on the development of earth abundant, sustainable catalytic
methods using early transition metals, and also on catalytic strategies for incor-
poration of CO2 into polymers. Prof. Tonks’ work has recently been recognized
with an Outstanding New Investigator Award from the National Institutes of
Health, an Alfred P. Sloan Fellowship, a Department of Energy CAREER award, and the ACS Organometallics
Distinguished Author Award, among others. Additionally, Prof. Tonks’ service toward improving academic
safety culture was recently recognized with the 2021 ACS Division of Chemical Health and Safety Graduate
Faculty Safety Award.
xii Editor Biographies
Timothy H. Warren is the Rosenberg professor and chairperson in the Depart-

ment of Chemistry at Michigan State University. He obtained his B.S. from the
University of Illinois at Urbana-Champaign in 1992 and Ph.D. from the Massa-
chusetts Institute of Technology in 1997. After 2 years of postdoctoral research at
the Organic Chemistry Institute of the University of Münster, Germany with Prof.
Dr. Gerhart Erker, Dr. Warren started his independent career at Georgetown
University in 1999 where he was named the Richard D. Vorisek professor of
chemistry in 2014. He moved to Michigan State University in 2021.
Prof. Warren’s research interests span synthetic and mechanistic inorganic,
organometallic, and bioinorganic chemistry with a focus on catalysis. His
research group develops environmentally friendly methods for organic synthesis
via C–H functionalization, explores the interconversion of nitrogen and ammo-
nia as carbon-free fuels, and decodes ways that biology communicates using nitric
oxide as a molecular messenger. Mechanistic studies on these chemical reactions catalyzed by metal ions such as
iron, nickel, copper, and zinc enable new insights for the development of useful catalysts for synthesis and
energy applications as well as lay the mechanistic groundwork to understand biochemical nitric oxide mis-
regulation. Dr. Warren received the NSF CAREER Award, chaired the 2019 Inorganic Reaction Mechanisms
Gordon Research Conference, and has served on the ACS Division of Inorganic Chemistry executive board and
on the editorial boards of Inorganic Synthesis, Inorganic Chemistry, and Chemical Society Reviews.
CONTRIBUTORS TO VOLUME 1
Matthew Asay Liang Deng

Universal Display Corporation, Ewing, NJ, United States State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese
R Tom Baker
Academy of Sciences, Shanghai, PR China
Department of Chemistry and Biomolecular Sciences and
Centre for Catalysis Research and Innovation, University Steven Fisher
of Ottawa, Ottawa, ON, Canada Lawrence Livermore National Laboratory, Livermore, CA,
United States
Isaac Banda
University of California Riverside, Riverside, CA, United Christophe Fliedel
States Laboratoire de Chimie de Coordination, UPR CNRS 8241,
Toulouse, France
Shilpa Bhatia
Department of Chemistry, University of Rochester, Jiaxin Gao
Rochester, NY, United States Department of Chemistry, University of California,
Riverside, CA, United States
Samuel M Bhutto
Department of Chemistry, Yale University, New Haven, Alexandre T-Y Genoux
CT, United States Department of Chemistry, Yale University, New Haven,
CT, United States
James D Blakemore
Department of Chemistry, University of Kansas, Lawrence, Nilay Hazari
KS, United States Department of Chemistry, Yale University, New Haven,
CT, United States
Chance M Boudreaux
Department of Chemistry, The University of Alabama, Wade C Henke
Tuscaloosa, AL, United States Department of Chemistry, University of Kansas, Lawrence,
KS, United States
Daniël LJ Broere
Organic Chemistry and Catalysis, Debye Institute Patrick L Holland
for Nanomaterials Science Faculty of Science, Department of Chemistry, Yale University, New Haven,
Utrecht University, Universiteitsweg 99, Utrecht, CT, United States
The Netherlands
Julie A Hopkins Leseberg
Matthew P Conley Department of Chemistry, University of Kansas, Lawrence,
Department of Chemistry, University of California, KS, United States
Riverside, CA, United States
Winn Huynh
Julia B Curley Department of Chemistry, University of California,
Department of Chemistry, Yale University, New Haven, Riverside, CA, United States
CT, United States
Errikos Kounalis
Sanjit Das Organic Chemistry and Catalysis, Debye Institute for
Department of Chemistry, The University of Alabama, Nanomaterials Science Faculty of Science, Utrecht
Tuscaloosa, AL, United States University, Universiteitsweg 99, Utrecht, The Netherlands
xiii
xiv Contributors to Volume 1
Vincent Lavallo Christopher GT Price

University of California Riverside, Riverside, CA, United Department of Chemistry, School of Life Sciences,
States University of Sussex, Brighton, United Kingdom
Richard A Layfield Aleksa Radovic
Department of Chemistry, School of Life Sciences, Department of Chemistry, University of Rochester,
University of Sussex, Brighton, United Kingdom Rochester, NY, United States
Nicholas E Leadbeater Jessica Rodriguez
Department of Chemistry, University of Connecticut, Department of Chemistry, University of California,
Storrs, CT, United States Riverside, CA, United States
Sergio Lovera Kavyasripriya K Samudrala
University of California Riverside, Riverside, CA, Department of Chemistry, University of California,
United States Riverside, CA, United States
Charles W Machan Weerachai Silprakob
Department of Chemistry, University of Virginia, Department of Chemistry, The University of Alabama,
Charlottesville, VA, United States Tuscaloosa, AL, United States
Moritz Malischewski S Chantal E Stieber
Freie Universität Berlin, Institut für Chemie Department of Chemistry & Biochemistry, California State
und Biochemie—Anorganische Chemie, Berlin, Polytechnic University, Pomona, CA, United States
Germany
Thomas S Teets
Sonya Manafe Department of Chemistry, University of Houston, Houston,
Department of Chemistry, The University of Alabama, TX, United States
Tuscaloosa, AL, United States
Varun Tej
Fernanda G Mendonça University of California Riverside, Riverside, CA, United
Department of Chemistry and Biomolecular Sciences States
and Centre for Catalysis Research and Innovation,
Siobhan R Temple
University of Ottawa, Ottawa, ON, Canada
Department of Chemistry, School of Life Sciences,
Maxime Michelas University of Sussex, Brighton, United Kingdom
Laboratoire de Chimie de Coordination, UPR CNRS 8241,
Anton W Tomich
Toulouse, France
University of California Riverside, Riverside, CA,
Zhenbo Mo United States
State Key Laboratory and Institute of Elemento-Organic
Tanya M Townsend
Chemistry, College of Chemistry, Nankai University,
Department of Chemistry, Yale University, New Haven,
Tianjin, PR China
CT, United States
Michael L Neidig
Jeremy E Weber
Department of Chemistry, University of Rochester,
Department of Chemistry, Yale University, New Haven,
Rochester, NY, United States
CT, United States
Aaron L Odom
C Gunnar Werncke
Department of Chemistry, Michigan State University,
Chemistry Department, Philipps-University Marburg,
East Lansing, MI, United States
Marburg, Germany
Elizabeth T Papish
Yanyu Wu
Department of Chemistry, The University of Alabama,
Department of Chemistry, University of Houston, Houston,
Tuscaloosa, AL, United States
TX, United States
Rinaldo Poli
Rowan D Young
Laboratoire de Chimie de Coordination, UPR CNRS 8241,
National University of Singapore, Singapore, Singapore
Toulouse, France
PREFACE
Published 40 years ago in 1982, the first edition of Comprehensive Organometallic Chemistry (COMC) provided an
invaluable resource that enabled chemists to become efficiently informed of the properties and reactions of
organometallic compounds of both the main group and transition metals. This area of chemistry continued to
develop at a rapid pace such that it necessitated the publication of subsequent editions, namely Comprehensive
Organometallic Chemistry II (COMC2) in 1995 and Comprehensive Organometallic Chemistry III (COMC3) in 2007.
Organometallic chemistry has continued to be vibrant in the 15 years following the publication of COMC3, not
only by affording compounds with novel structures and reactivity but also by having important applications
in organic syntheses and industrial processes, as illustrated by the awarding of the 2010 Nobel prize to Heck,
Negishi, and Suzuki for the development of palladium-catalyzed cross couplings in organic syntheses. Compre-
hensive Organometallic Chemistry IV (COMC4) thus serves the same important role as its predecessors by
providing an indispensable means for researchers and educators to obtain efficiently an up-to-date analysis of
a particular aspect of organometallic chemistry.
COMC4 comprises 15 volumes, of which the first provides a review of topics concerned with techniques
and concepts that feature prominently in current organometallic chemistry, while 5 volumes are devoted to
applications that include organic synthesis, materials science, bio-organometallics, metallo-therapy, metallo-
diagnostics, medicine, and environmental chemistry. In this regard, we are very grateful to the volume editors
for their diligent efforts, and the authors for producing high-quality chapters, all of which were written during
the COVID-19 pandemic. Finally, we wish to thank the many staff at Elsevier for their efforts to ensure that the
project, initiated in the winter of 2018, remained on schedule.
Karsten Meyer, Erlangen, March 2022
Dermot O’Hare, Oxford, March 2022
Gerard Parkin, New York, March 2022
xv
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1.01 Introduction: Volume I
Patrick L Holland, Department of Chemistry, Yale University, New Haven, CT, United States
© 2022 Elsevier Ltd. All rights reserved.
The field of organometallic chemistry has undergone substantial evolution since the publication of the original Comprehensive
Organometallic Chemistry in 1982, and even since the appearance of Comprehensive Organometallic Chemistry III in 2007. This
has encouraged us to compile a fresh version of Volume 1 that introduces the reader to cross-cutting concepts that are involved in
the subsequent volumes. The topics have been chosen to minimize overlap with the chapters in Volume I of Comprehensive
Organometallic Chemistry III, and to highlight emerging areas. For example, valence bond theory models for understanding
bonding have been used increasingly due to their intuitive content (Odom), and the popularization of redox-active ligands
(Broere) has encouraged organometallic chemists to look beyond the formal oxidation state. Chemists have continued to push
the boundaries of oxidation states with highly oxidized (Malischewski) and highly reduced (Werncke) complexes, which display
amazing reactivity as well. In organometallic chemistry, chemists also strive toward the binding and activation of weak substrates
like alkanes (Young), carbon dioxide (Machan), and dinitrogen (Holland). Growing attention to the use of abundant first-row
metals has fed a renaissance of paramagnetic organometallic complexes and advanced spectroscopic techniques, which are covered
in chapters on computations (Stieber) and on spectroscopy (Neidig). Organometallic chemistry has remained largely driven by
ligand design, and a number of chapters explore popular ligand types such as N-heterocyclic carbenes (Deng) and ligands
with charge separated from the metal (Lavallo). In addition, influences from outside the coordination sphere are increasingly
utilized, and accordingly we include chapters on organometallic systems that incorporate Lewis acid participation (Hazari),
proton-responsive ligands (Papish), and attachment to oxide surfaces (Conley). The use of organometallic complexes has also
expanded in non-traditional applications like electrochemistry (Blakemore), single-molecule magnets (Layfield), photosensitizers
(Teets), and radical reactions (Poli). Finally, practical considerations in catalysis have fueled research into strategies for hetero-
genization and separation (Baker), and on principles that help the chemist to recognize spurious results from catalyst impurities
(Leadbeater).
Construction of these extensive reviews requires an immense amount of effort, and all organometallic chemists owe a debt of
gratitude to these generous authors for the time they devoted to teaching us about modern aspects of organometallic chemistry.
They have all thoughtfully revised to incorporate my suggestions for clarification, and I am confident that the resulting chapters give
insights and trends that will guide the next generation of organometallic chemists to even greater heights.
Comprehensive Organometallic Chemistry IV https://doi.org/10.1016/B978-0-12-820206-7.00166-9 1

1.02 Models for Understanding Main Group and Transition Metal Bonding
Aaron L Odom, Department of Chemistry, Michigan State University, East Lansing, MI, United States
© 2022 Elsevier Ltd. All rights reserved.
1.02.1 Introduction 2
1.02.2 Primogenic repulsion: Orbital size effects in bonding in the periodic table 2
1.02.3 The 2-center 2-electron heterocovalent bond and polar covalence theory 5
1.02.4 The 2-center 2-electron dative bond 12
1.02.5 Complementarity of qualitative hybridization theory and molecular orbital theory 14
1.02.6 Lone pair bond weakening and its influence on organometallic chemistry 18
1.02.7 Beyond the 2-center 2-electron bond 20
1.02.8 Examples of using Bent’s rule, hybridization, and structure in the main group 23
1.02.9 Hybridization theory and the transition metals 25
1.02.10 Practical evaluation of metal-ligand bond interactions for applications in catalysis 27
1.02.11 Concluding remarks 29
Acknowledgments 29
References 29
1.02.1 Introduction
Structure is a central concept that defines and empowers function in biology, chemistry, and physics. Pauling said, “The whole
problem of understanding science is, I believe, the problem of relating facts to the concept of structure, first in terms of atoms and
then in terms of something still smaller, such as nucleons . . . It is structure that we look for whenever we try to understand anything.
All science is built upon this search: we investigate how the cell is built of reticular material, cytoplasm, chromosomes; how crystals
aggregate; how atoms are fastened together; how electrons constitute a chemical bond between atoms. We like to understand, and to
explain, observed facts in terms of structure.”1
Structure for beginners in chemistry usually consists of viewing molecules with a “hub and strut” model, where the atoms act as a
hub in the structure connected by bonding struts represented by lines. Upon this basis, we add layers of complexity depending on
the types of atoms and bonds, but molecular structure remains the basis of our models for understanding electronic structure,
reactivity, and properties.
The atomic “hubs,” from a chemical perspective, are often quite adjustable, and the same element may vary dramatically in the
number and types of bonds from one compound to the next. What chemists mean by a line between atoms is also wonderfully
diverse, rich, and complex as well. Because a full quantum-mechanical treatment is complex and difficult to conceptualize,
organometallic chemists seek simpler models that are more intuitive, yet grounded in quantum mechanics. These simpler
expressions of nature may have limitations, but as Roald Hoffmann said, “Chemistry is not mathematics, and even if it bothers
some people like hell, there are no theorems of chemistry. Chemical arguments are not falsified by an exception.”2 If one
approximation for understanding the bonding fails, we attempt to use a better (sometimes just as simple, sometimes more
complex) approximation to understand the system.
This chapter is a perspective on “what the lines mean” in some chemical structures. It focuses on relatively simple models for
understanding bonding that are readily applied, as these more often help one design the next experiment. This seems fitting, as said
in a recent review by Schwerdtfeger, Frenking, and coworkers (emphasis theirs), “Chemical bonding models are not right or wrong, they
are more or less useful.”3 In addition, some fundamental principles will be covered that are beneficial for understanding bonding
throughout the periodic table. There will be little discussion of historical context, basics of molecular orbital theory, and other topics
that are common to undergraduate texts. What is covered will be no less fundamental, but the attempt is made to boil down the
discussion to a few (largely pen and paper) models the author finds particularly helpful; these are sometimes supplemented with
quantum chemical results, e.g., density functional theory (DFT) and natural bond orbital (NBO) calculations.
1.02.2 Primogenic repulsion: Orbital size effects in bonding in the periodic table
We start with the task of explaining the “primogenic effect,” which will clarify: why the 1st row is so different from the rest of the
p-block; why the 1st row transition metals show different behavior (e.g., weaker bonds and weaker ligand fields) than the 2nd and
3rd row; and why the lanthanides show little f-orbital participation in bonding while the actinides show significantly more.
2 Comprehensive Organometallic Chemistry IV https://doi.org/10.1016/B978-0-12-820206-7.00100-1

Models for Understanding Main Group and Transition Metal Bonding 3
Before describing this effect, we need to review three simple ideas:
(1) All the atomic orbitals of an atom are orthogonal to one another. This orthogonality is maintained, not through spatial
separation, but through cancelation of bonding and antibonding interactions. The net overlap of any atomic orbital with
another is zero due to this cancelation.
(2) This orthogonality is maintained through a combination of angular and radial nodes. The 1s orbital, for example, maintains
orthogonality with the 2s orbital because the 2s orbital has a node, a change of sign in the wave, so that the two orbitals have no
net overlap. (More on this to follow.) For angular differences, the cancelation is readily seen in say the overlap of a p orbital with
an s on the same atom (Fig. 1). The constructive overlap, unshaded with unshaded, is exactly canceled by the destructive
overlap, unshaded with shaded, which is true of any combination of orbitals with different angular momentum on the same
atom.
(3) Finally, it is useful to have an expectation for the size of orbitals of different angular momentum with the same principal
quantum number (n). For example, when n ¼ 4 there are 4s, 4p, 4d, and 4f orbitals. Which orbital do we expect to be the
smallest and which the largest in radius? The angular momentum quantum number l corresponds to the shape of the orbital,
with shapes having greater curvature being associated with higher angular momentum. Thinking from a classical perspective for
a moment, we can model the electron’s motion around the nucleus as a ball (electron) rotating on an elastic string (Coulombic
attraction to the nucleus). If we increase the angular momentum, the elastic string should stretch further from the central point.
In other words, we expect that the 4s orbital, which has a lowest angular momentum, would be most compact (closest to
nucleus) while the 4f orbital, which has the highest angular momentum, would be the most diffuse (farthest from nucleus).
When comparing filled orbitals with the same principal quantum number, lower angular momentum orbitals are expected to
have smaller radii.
The term “primogenic repulsion” was first published by Pyykkö in 1979,4 and he attributed the phrase to a colleague in the
Department of English. The primogenic effect refers to the ability of orbitals of a specific angular momentum appearing for the first time in the
Aufbau sequence, i.e., 1s, 2p, 3d, and 4f, to shrink towards the nucleus more than might be expected, simply because there are no orbitals of
the same angular momentum in the core below them. All orbitals in a particular shell are orthogonal by their shape due to the l and ml
quantum number differences (vide supra). By this principle, most orbitals then have their size set, to some extent, by the necessity of
being orthogonal to the orbitals of the same angular momentum below them. In other words, the size of the 1s-orbital affects the
size of the 2s orbital; the 2s must have its node fit precisely with the 1s so that there is zero overlap. If the 1s orbital contracted, the
2s orbital would also have to contract. In contrast, the 2p orbitals, because there is no “1p orbital,” have no such restriction and can
lower their energy by contracting toward the nucleus.5,6
Fig. 1 Atomic orbitals of different angular momentum are always orthogonal with equal amounts of constructive and destructive interference. As an example, (top)
a 1s orbital and 2p orbital on the same atom have equal amounts of constructive (unshaded with unshaded) and destructive (unshaded with shaded) interference.
(Bottom) The 1s and 2p wavefunctions are plotted. Centered around the origin (nucleus), the constructive interference (right of the origin) is equivalent to the
destructive interference (left of the origin).
4 Models for Understanding Main Group and Transition Metal Bonding
The result of the 2p-orbital contraction, and primogenic expansion of 2s, is that the 2s and 2p orbitals for the first-row p-block
elements are essentially the same size. (For the rest of the p-block, the valence s-orbital is about 80% the size of p because both
orbitals are primogenically expanded and p has a higher angular momentum.) Since the 2s and 2p orbitals are similar in size, they
more effectively hybridize than, for example, 3s and 3p. Thus, the directional bonding and multiple bonding that dominate organic
chemistry are due in large part to the primogenic effect.
To illustrate, consider the very familiar geometry of acetylene versus Ar–GeGe–Ar (Fig. 2).7 While acetylene has the familiar
linear geometry with sp hybridization on carbon, all the heavier congeners are bent. The experimental geometry of the germanium
complex has Ge–Ge–Ar angles of 128.7(1) , closer to that expected for sp2 than sp. Natural Bond Orbital calculations on the
H–GeGe–H model compound (Fig. 2) identify the hybridization of the orbital used by germanium to form the Ge–Ge s-bond as
essentially sp; however, the Ge–H bond is formed by an sp2 hybrid, which gives a bent geometry. The primogenic effect limits the sp
hybridization somewhat for the heavier congener, giving a preference for bonding with greater p character. (This is only part of the
answer as the lower electronegativity of the elements below carbon also affects the hybridization, Bent’s Rule, vide infra.)
There are many other common chemical observations that may be attributed to primogenic repulsion, or lack thereof.
Of particular importance for our purposes here is the contraction of the 3d orbitals of the first row of the transition series. The
3d orbitals are smaller than might be expected from their heavier congeners. As a result, the 3d orbitals are only about 1/3 the size of
the valence 4s-orbitals for these metals.8 In addition, the 3d-orbitals are very close to the same size as the core 3p orbitals; for
example, the 3p-orbitals of iron have radiia of 0.373 Å, while the 3d orbitals have radii of 0.364 Å, slightly smaller than these core
orbitals.8 So, as ligands approach the metal for bonding with the 3d orbitals, there is repulsion by core orbitals of essentially the
same size. The relationship between the 3d and 3p orbitals for the first-row d-block elements is shown in Fig. 3. The early transition
metals have d-orbitals slightly extended from the core, while the later metals have valence d-orbitals slightly smaller than these core
orbitals.
In contrast to the first-row transition metals, the second and third row elements have d orbitals that extend well beyond the core.
For example, ruthenium has 4d orbital radii of 0.616 Å, while the 4p orbitals are smaller at 0.515 Å. The sizes of these orbitals
are shown in Fig. 4, and the valence 4d-orbitals are always larger than the core orbitals for the elements. (The third-row metals are
slightly larger but provide similar ratios: e.g., osmium has 5d-orbials with radii of 0.682 Å, with 5p radii of 0.550 Å.)
An important consequence of primogenic repulsion on the valence orbitals for the 2nd and 3rd row transition elements, and the
lack thereof for the 1st row, is that the bonds formed by the heavier congeners are stronger than the 1st row for similar compounds.
The small size and core repulsion effects in the 1st row result in relatively weak bonds and weaker ligand fields than found for the
2nd and 3rd rows.
128.7(1)° 124.0°
H Ar
C Ge Ar Ge
C Ge Ge
H Ar Ar
Carbon has sp-hybridization Experimental Calculated

geometry of Ge2Ar2 geometry of Ge2H2
Ge
Ge
Fig. 2 (Top left) The familiar geometry of acetylene, which has sp-hybridized carbons due to good hybridization between 2s and 2p, a result of the primogenic
effect. (Top center and bottom) Line drawing and ORTEP diagram from the X-ray diffraction data on Ar–GeGe–Ar, where Ar ¼ 2,6-(2,6-diisopropylphenyl)phenyl.
(Top right) The calculated geometry of H–GeGe–H using M06L/aug-cc-PVTZ on G19. Ar ¼ 2,6-(2,6-Pri2C6H3)2C6H3.
a
Waber and Cromer calculated the “maximum in the charge density and its corresponding radius” for the atomic valence orbitals, which I’ll simply refer to as the
“orbital radius.”8
Fig. 3 The sizes of the valence 3d (red) and core 3p-orbitals (blue) for the first-row transition elements.8
Fig. 4 The sizes of the valence 4d (orange) and core 4p-orbitals (light blue) for the second-row transition elements.8
The primogenic effect dramatically affects the chemistry of the f-block as well. The f-orbitals of the lanthanides contract toward
the nucleus so that they are less than 20% the size of the valence s-orbital, far smaller than some of the core orbitals. For example, for
cerium, the f-orbitals are 0.366 Å, while the core 5p-orbital is over twice as large at 0.825 Å. As a result, the f-orbitals of the
lanthanides are so small that they often cannot overlap with ligand orbitals and are rarely involved in bonding. In contrast, the
actinides have primogenically expanded 5f-orbitals that may participate in bonding.8
1.02.3 The 2-center 2-electron heterocovalent bond and polar covalence theory
A series of concepts we are taught from our initial indoctrination as chemists regard covalent 2-center 2-electron (2c2e) bonds, such
as those found in H2 and HCl. According to Molecular Orbital (MO) theory, championed by Mulliken, overlap leads to bonding
and antibonding molecular orbitals where the lower energy bonding orbital is occupied. In Hybridization theory, championed by
Pauling, the bond is viewed as a series of resonance forms, with some ionic contributions. In the end, the two viewpoints are
mathematically equivalent at their limits,9 and the choice of one model over the other is based on expediency in addressing the
problem at hand.
Pauling was such an effective advocate that Valence Bond (VB) theory was regarded as the “correct” method for understanding
chemical bonding until there was a series of instances where VB theory was thought to fail to give the correct answer where MO
theory was successful. Common examples where VB theory was thought to fail are in describing the electronic structure of O2 and
photoelectron spectrum of CH4. In actuality, these “failures” of VB theory are attributable more to poor use of the theory than the
theory itself.10,11
A major advantage of VB theory is that the localized bonds are more easily correlated with the lines in our Lewis structures than
delocalized molecular orbitals of MO theory. Despite this advantage, VB theory fell out of favor because MO theory was easier to
adapt to computational methods. Computers were powerful allies to MO theory, leaving VB methods behind for many years.
In some ways related to the orbitals used in VB theory, Natural Orbitals were first discussed by Löwdin in 1955, but Weinhold
and Landis turned them into a powerful tool for modern chemists. Effectively, Natural Bond Orbital (NBO) theory allows the use of
modern computation methods (DFT, coupled cluster theory, etc.) to adopt many advantages of VB theory. In this chapter, I will refer
to “Hybridization theory” as a general term that incorporates the underlying concepts of VB and NBO theory. The underlying
conceptual underpinnings of VB theory (and NBO theory) regain relevance as quantitative methods can be used in conjunction with
the back-of-the-envelope calculations.
In this section, it is advantageous to outline a Hybridization theory system for understanding heterocovalent bonds, Polar
Covalence theory. The theory is not put forward as a replacement for accurate quantum mechanical calculations or experimental
bond energies. Instead, it is a method for calculating bond energies by hand that illustrates several important concepts about
bonding. No derivations of the equations are given to provide room for a discussion of concepts that underlie these descriptions of
covalent bonds.
Polar Covalence theory was developed by R. T. Sanderson as a method for the calculation of bond energies.12,b The method uses
only a few descriptors for the elements and the bond distance, R0, in the compound to calculate the bond energy, typically within
5% of experimental values. The tabulated values are Sanderson electronegativity (wS), the change in electronegativity of an
element with unit charge (DwS), covalent radii (rc), and the homonuclear bond energies of the elements. The homonuclear bond
energies are described as being “fully unweakened” (E000 ), “partially weakened” (E00 ), and “fully weakened” (E0 ). A selection of these
values is shown in Table 1.
The cause of the weakening (difference between E000 , E00 , and E0 ) is a very interesting one that explains many chemical
phenomena. Unfortunately, it will also require some building of foundations before the explanation can be given and the cause
described. For the moment, we will call it Lone Pair Bond Weakening (LPBW), which was Sanderson’s name for the effect, an effect
that wasn’t fully elucidated until 1996.15
On the surface, Sanderson electronegativity (wS) has nothing to do with bond energies to the element, unlike Pauling
electronegativity, which is derived from bond energies. In contrast, Sanderson electronegativity is derived from electron density
of the atoms (z) and their relationship to a calculated ideal electron density (zi). The electron density around the atom is simply as
shown in Eq. (1). The electron density of an atom X is the atomic number divided by the volume of the sphere defined by the
covalent radius of the atom in units of electrons/Å 3.
Z e
zX ¼ 4 3 3 (1)
3 pr Å
The ideal electron density was found by making an interesting assumption. It was assumed that the noble gases were not only
unreactive because of a closed shell, but also because they had an ideal electron density around the atom. The ideal electron density
(zi) for non-noble gas atoms was found by linear interpolation between the nearest noble gases; in other words, the two noble gases
that are the bookends for an atomic shell were used to define a line of electron density relative to atomic number that was ideal for
the atoms in between.
Sanderson electronegativity is simply the ratio between the electron density of an atom (z) and the ideal electron density (zi), i.e.,
wS ¼ (z)/(zi). Originally, these values were called “stability ratios” as they gave a measure of how the atom could be stabilized by
addition or subtraction of electron density, and fluorine had a value of 5.75 on this scale. Later, Sanderson scaled all his values to the
more familiar Pauling value of wF ¼ 4.00, and the numbers became known as Sanderson electronegativity.16
At this stage, the equations for determination of bond energies using Polar Covalence theory will be given (Table 2) and a brief
explanation of each will be provided with the underlying concept.
As mentioned, Polar Covalence theory is based on Hybridization theory and suggests that the bond in a heterocovalent
compound can be described using only two resonance forms (Fig. 5). In the left form, there is a purely covalent bond between
atoms A and X, signified by a line. In the right form, there is a purely ionic form where the less electronegative atom (A) has a
positive charge, and the more electronegative atom (X) has a negative charge. An alternative, minor, resonance form where the less
electronegative atom has a negative charge is disregarded.
The overall bond energy (the average enthalpy of the bonds in the compound) according to Polar Covalence theory is comprised
of the covalent bond energy, Ec, and the ionic bond energy, Ei, with two weighting coefficients tc and ti. The sum of the contributions
from all resonance forms should be unity, and these are the only forms being considered, so tc +ti ¼ 1 (Eq. 3 in Table 2). The overall
b
Here, “bond energy” refers to the average bond enthalpy for homolytic cleavage of the bonds in a compound, e.g., 1/3 of the enthalpy required to atomize
BF3 to B + 3 F. A more detailed explanation and examples are given below.
Table 1 Sanderson electronegativities (wS), change in electronegativity with unit charge (D wS), covalent radii (rc) in Å ( 10−10 m), homonuclear fully
unweakened (E000 ), partially weakened (E00 ), and fully weakened (E0 ) bond energies in kcal/mol.a
pffiffiffiffiffi
Element wS DwS ¼ 1:57 wS Rc E000 E00 E0
H 2.592 2.528 0.320 104.2

Li 0.670 1.285 1.336 24.6
Be 1.810 2.112 0.887 67.6
B 2.275 2.368 0.822 76.7
C 2.746 2.602 0.772 85.4
N 3.194 2.806 0.734 94.9 66.9 38.8
O 3.654 3.001 0.702 104.0 68.8 33.6
F 4.000 3.140 0.681 113.1 76.8 38.2b
Na 0.560 1.275 1.539 16.4
Mg 1.318 1.802 1.373 42.3
Al 1.714 2.055 1.258 48.2
Si 2.138 2.296 1.169 54.1
P 2.515 2.490 1.107 60.0 56.9 53.7
S 2.957 2.700 1.049 65.9 60.4 54.9
Cl 3.475 2.927 0.994 71.8 64.9 58.0
K 0.445 1.047 1.962 13.1
Ca 0.946 1.527 1.74 30.8
Sc(II) 0.64 1.256 1.695 31.3
Sc(III) 1.02 1.586 1.695 31.3
Ti(II) 0.73 1.341 1.650 31.8
Ti(III) 1.09 1.639 1.650 31.8
Ti(IV) 1.50 1.923 1.650 31.8
V(II) 0.69 1.304 1.605 32.3
V(III) 1.39 1.851 1.605 32.3
V(IV) 1.89 2.158 1.605 32.3
V(V) 2.51 2.487 1.605 32.3
Cr(II) 1.24 1.748 1.560 32.8
Cr(III) 1.66 2.023 1.560 32.8
Cr(IV) 2.29 2.376 1.560 32.8
Cr(V) 2.83 2.641 1.560 32.8
Cr(VI) 3.37 2.882 1.560 32.8
Mn(II) 1.66 2.023 1.516 33.3
Mn(III) 2.20 2.329 1.516 33.3
Mn(IV) 2.74 2.599 1.516 33.3
Mn(V) 3.28 2.843 1.516 33.3
Mn(VI) 3.82 3.069 1.516 33.3
Fe(II) 1.64 2.011 1.471 33.8
Fe(III) 2.20 2.329 1.471 33.8
Co(II) 1.96 2.198 1.426 34.3
Co(III) 2.56 2.512 1.426 34.3
Co(IV) 3.10 2.764 1.426 34.3
Ni(II) 1.94 2.187 1.381 34.8
Ni(III) 2.73 2.594 1.381 34.8
Ni(IV) 3.27 2.839 1.381 34.8
Ni(V) 3.81 3.065 1.381 34.8
Cu(II) 1.98 2.209 1.336 35.3
Zn 2.223 2.341 1.292 35.8
Ga 2.419 2.442 1.256 40.3
Ge 2.618 2.540 1.223 44.8
As 2.816 2.635 1.294 49.3 45.1 40.9
Se 3.014 2.726 1.167 53.8 46.0 38.2
Br 3.219 2.817 1.142 58.3 52.2 46.1
Rb 0.312 0.877 2.16 12.4
Sr 0.721 1.333 1.91 24.6
Y(II) 0.40 0.993 1.868 25.1
Y(III) 0.65 1.266 1.868 25.1
Zr(II) 0.52 1.132 1.826 25.7
Zr(III) 0.79 1.395 1.826 25.7
Zr(IV) 0.90 1.489 1.826 25.7
Nb(II) 0.77 1.378 1.784 26.3
Nb(III) 1.02 1.586 1.784 26.3
Nb(IV) 1.25 1.755 1.784 26.3
(Continued )
Table 1 (Continued)
pffiffiffiffiffi
Element wS DwS ¼ 1:57 wS Rc E000 E00 E0
Nb(V) 1.42 1.871 1.784 26.3

Mo(II) 0.90 1.489 1.742 26.9
Mo(III) 1.15 1.684 1.742 26.9
Mo(IV) 1.40 1.858 1.742 26.9
Mo(V) 1.73 2.065 1.742 26.9
Mo(VI) 2.20 2.329 1.742 26.9
Cd 1.978 2.208 1.493 30.4
In 2.138 2.296 1.455 33.1
Sn(IV) 2.298 2.380 1.420 35.8
Sn(II) 1.477 1.908 1.420 35.8
Sb 2.458 2.461 1.389 38.5 35.8 33.0
Te 2.618 2.540 1.360 41.2 39.2 37.2
I 2.778 2.617 1.333 43.9 40.0 36.1
Cs 0.220 0.736 2.35 10.8
Ba 0.651 1.267 1.98 22.2
Hf(II) 0.31 0.874 1.80 15.6
Hf(III) 0.56 1.175 1.80 15.6
Hf(IV) 0.81 1.413 1.80 15.6
Ta(II) 0.44 1.041 1.76 14.7
Ta(III) 0.69 1.304 1.76 14.7
Ta(IV) 0.94 1.522 1.76 14.7
Ta(V) 1.17 1.698 1.76 14.7
W(II) 0.73 1.341 1.73 13.8
W(III) 0.98 1.554 1.73 13.8
W(IV) 1.23 1.741 1.73 13.8
W(V) 1.48 1.910 1.73 13.8
W(VI) 1.67 2.029 1.73 13.8
Tl(III) 2.246 2.353 1.490 16.6
Tl(I) 0.98 1.560 1.49 16.6
Pb(IV) 2.291 2.376 1.48 24.2
Pb(II) 1.900 2.164 1.48 24.2
Bi 2.342 2.403 1.47 32.2
a
Values are from Sanderson’s references on Polar Covalence.12,13
b
Value from Huber and Herzberg.14
Table 2 Polar Covalence Theory equations for determining homolytic bond energies.
Determination of the A–X bond energy EA−X ¼ tcEc + ttEt (2)a

Sum of the ionic and covalent coefficients is unity 1 ¼ tc + tt (3)
pffiffiffiffiffiffiffiffiffiffiffiffiffi
Covalent bond energy E c ¼ b RR0c E AA E XX (4)b
Rc ¼ RA + RX
Bond order b
Single 1.000
Double 1.488
Triple 1.787
Ionic bond energy E i ¼ b 332 kcalÅ=mol (5)

R0 Å
Estimation of the ionic coefficient t t ¼ jdA j 2+jdX j (6)c
Charge on an atom in a molecule dA ¼ ð1:57
wM −wA Þ ðw −w Þ
pffiffiffiffi ¼ M A (7)d
wA DwA
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
Molecular electronegativity N A B Z (8)e
wm ¼ wA wB ⋯ wNZ
N N
a
tc ¼ covalent coefficient, ti ¼ ionic coefficient, Ec ¼ covalent bond energy, Ei ¼ ionic bond energy.
b
Rc ¼ covalent bond distance from sum of covalent radii (RA + RX), R0 ¼ bond distance, EAA ¼ covalent bond energy of A,
EXX ¼ covalent bond energy of X.
c
d ¼ partial charge.
d
wM ¼ molecular electronegativity, wA ¼ electronegativity of A.
e
N ¼ number of total atoms, NA ¼ number of atoms A.
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animals and plants in order to live, so that we can further extend our
altruism at most to a moderate protection of other animals, if we are
to avoid injury to our own race. We may remark in passing that the
altruism of many lovers of animals, who prefer their favourite pets to
human beings and to the social welfare, is typical of the
exclusiveness and stupidity of misdirected impulses of sympathy.
Morality must therefore in the future consist of a common social
impulse—it must itself become social. This impulse must overthrow
not only egotism, but also the exclusiveness of individual
sympathies. We are still, alas, far from this goal! The family is often a
thieves’ kitchen; patriotism is a prolific parent of wars; while
communities and societies, however noble their objects may be,
readily degenerate into petty sects and cliques.
And now comes yet another difficulty, namely, the frequent lack of
harmony between the ethical motives which inspire an action and its
real moral value.
“Ich bin
Ein Theil von jener Kraft
Die stets das Böse will
Und stets das Gute schafft,”
says Mephistopheles in Goethe’s Faust.[B] Let us say often instead of

always, and mention also that other Power which often wills the good
and yet does the evil, and we have the well-known picture of the
intelligent, ambitious egotist, who, without any sense of duty,
achieves great and good results; and that of the foolish, infatuated
altruist, who devotes the whole might of his zeal for duty to the
service of socially pernicious forces!
[B] “I am a part of that power which always wills the evil and
always does the good.”
As a result of exaggerating the above-mentioned phenomena

certain theorists have imagined that ethics can be founded upon
pure egotism. But this is a mistake. Without the altruistic impulses of
sympathy and duty among its individual members no common social
existence can thrive; on the contrary, it must degenerate.
The power of the emotions in man is much too strong to allow of
any other result. Any one who imagines that he is completely master
of his emotions makes, if possible, a still greater mistake than one
who avows that he has never lied, or that his actions are governed
by free-will. All human morality is bound up with these impulses and
emotions. Socialism, for instance, will become moral, or else it will
not come to pass. Without the support of the social conscience of
mankind it cannot become moral. Every effort must therefore be
directed towards strengthening the social conscience.
The falsity of the theory of absolute good and evil is demonstrated
by the whole disposition of a world in which living creatures are
designed to prey upon one another. When a spider devours a fly it is
good for the spider and bad for the fly. The ethical value of the act
itself is therefore purely relative.
It is just the same with human ethics. To attempt to explain all the
evil in the world by the sin of Adam is to attribute a miserable
incapacity to God. The same holds true of the attempts of certain
modern Protestants to set up the dogma of a progressive revelation,
in order to bring the older dogmas into harmony with the theory of
evolution and descent. All these halting exegeses are only new
models of the artificial drags which theology seeks to impose upon
the free research of science.
Altruism and egotism stand only in relative opposition. Among ants
and bees they are instinctively adjusted to one another with
wonderful harmony, and are rarely, if ever, found in conflict. This
result can and must be striven after by mankind, however great may
be the difficulties presented by our hereditary nature. For its
achievement a harmonious co-operation of the hereditary social
conscience with reason and knowledge is absolutely necessary.
I must briefly mention two other points. Firstly, morality and social
or race hygiene become one and the same thing directly we include
in our conception of hygiene a healthy condition of the brain or soul,
and subordinate the individual hygiene to that of society in general.
Then everything socially unhygienic is immoral, and everything
immoral socially unhygienic. If, for instance, I ruin a healthy, active
member of society, in order possibly to achieve the salvation of an
incurably diseased criminal, I am committing, although from altruistic
motives, an act which is injurious from the point of view both of
ethics and social hygiene, and therefore evil and immoral.
Secondly, the boundaries of jurisprudence and of ethics are by no
means clear. Jurisprudence is more narrowly confined. It has no right
to lay claim to or to pass a verdict upon everything which ethics may
discover or attain. Laws and the constraint they imply are a
necessary evil, a crutch for the lame and defective social
conscience. They must be reduced to an indispensable minimum.
The ethical and social instincts, on the other hand, can never be too
highly developed. Humanity must gradually develop in the future to
such a point that jurisprudence may be completely replaced by an
instinctive and inculcated social impulse.
“Es erben sich Gesetz und Rechte

Wie eine ew’ge Krankheit fort.”[C]
[C] “Laws and statutes pass on in heritage, like an eternal

disease.”—Goethe, Faust.
In order now properly to understand our actual subject, viz. sexual
ethics, we must state the fact that an action, as well as the motives
which inspire it, may be either (1) ethically positive, i.e. good; (2)
ethically negative, i.e. evil; or (3) ethically indifferent, i.e. without any
relation to morals.
In their relationship to morals an action and its motive may be
completely independent of one another, as we have already seen.
We must further note that there are various degrees of duty, and
that from this cause conflicts may arise. There are duties towards
one’s self, which serve to increase the worth, and particularly the
social worth, of the individual by self-culture and education. In these
days of effeminate culture it is too often forgotten that self-discipline
and restraint, and even a certain degree of asceticism, fit the
individual for freedom and happiness, while the craving for pleasure
makes him useless and dependent.
Then there are duties towards the family and those nearer to us,
towards the State, towards existing Humanity, and towards posterity.
This last duty is the highest of all. Everything that we enjoy to-day in
culture and knowledge we owe to the toil, the suffering, and often the
martyrdom of our forefathers. Our most sacred duty is, therefore, to
secure for our descendants a loftier, happier and worthier existence
than our own.
Speaking generally, a rational system of morals must subordinate
the welfare of the individual to that of the community at large. A man
who is unprejudiced and possesses the ethical and social instinct will
therefore hold it as a principle first of all to do no man any injury;
then to develop his own individuality as highly as possible, which will
be both for his own good and that of the community; and as far as in
him lies to be of service to others and to Humanity.
From this we may derive the following commandment of sexual
ethics:—
Thou shalt take heed in thy sexual desire, in its manifestations in
thy soul, and chiefly in thy sexual acts, that thou do no hurt to thyself
nor another, nor, above all, to the race of men; but shalt strive with
thy might to increase the worth of each and all.
II. Sexual Ethics
Everything that we have up to the present said of ethics and the
social sense in general applies also to sexual ethics in particular.
The only essential thing is to discuss the matter without prejudice,
and to put aside the ancient traditions of mystagogy, dogma, and
custom. This should be comparatively easy when we consider our
present-day conventions, hypocritical as they are to the point of
nausea, and the manner in which they support the right of the
stronger and other rank abuses under the false cloak of morality.
In itself the sexual desire is neither moral nor immoral. It is simply
an instinct adapted to the reproduction of the species. The common
confusion of sexuality with immorality is, I repeat, entirely erroneous.
A man without sexual feeling must of course be extraordinarily
“moral” in his sex relationships, and yet he can be the greatest
scoundrel imaginable. His sexual coldness and indifference have not
the smallest ethical value.
According to the definition given above, we may classify every
sexual desire as ethically positive if it is of benefit to individuals, to
society, and especially to the race (that is, to posterity); as ethically
negative if it does injury to any or all of these; and as ethically
indifferent if it neither does injury nor is of any service. At the same
time we must observe the ethical gradation: (1) the race, (2) society,
(3) the more intimate surroundings or family, and (4) the individual
self.
When we come to examine the concrete cases more closely we
find that the circumstances attendant upon the gratification of the
sexual desire, and the consequences of this gratification, lead to
conflicts with morality far more frequently than does the sexual act
itself.
In the first place even the normal reproduction of human beings
may become immoral, in that it may do injury to the race or to
individuals. Malthus pointed out this fact. Habitable space upon the
earth is limited, while, on the other hand, the procreative capacity of
mankind is unlimited. If unlimited reproduction is permitted, it is
possible that the existing space may be insufficient to meet the
needs of the enormous multitudes of men which must result. The
latter may then fall victims to famine and distress, as in the case of
the Chinese, or the rabbits of Australia; and only disease, starvation,
or slaughter can bring about a return to the normal condition. It must
be obvious to every unbiassed person that this is not moral. And as
there are harmless methods of regulating the number of births and to
some extent the quality of the offspring, the just and proper use of
these methods must be described as ethically positive. Everything is
moral which makes for the happiness and well-being of society;
everything immoral which prejudices or endangers it.
There can, however, be too few people in the world; and there is
everywhere a great dearth of men and women wholly sound in mind
and body, light-hearted, unselfish, industrious, persevering,
intelligent, able and yet well-intentioned, peaceable, and honest.
On the other hand, we have a monstrous superabundance of
feeble, sickly, mentally perverted, criminally disposed, idle,
treacherous, vain, crafty, covetous, passionate, capricious, and
untrustworthy individuals, whose claims upon others are
inexhaustible, while their own services to society are either valueless
or actually harmful.
While the first-mentioned class produce far more than they
consume, it is appalling to think of the vast store of human energy
and human life which goes to waste in sick-rooms, lunatic asylums,
hospitals, and prisons. And if we look more closely we find outside
these institutions, and under no restraint, a still vaster army of
human sharks, who prey physically and mentally upon society, and
are a burden upon the industrious community. The greater number of
these useless pests owe their faults to an hereditarily defective
constitution of the protoplasmic germs which brought them into
being; and therefore a sound system of racial ethics demands
rational selection in breeding.
Equally destructive, however, are external conditions and habits of
life, such as the use of alcohol, resulting as they do in paralysis of
energy, confusion of the mind, and degeneration of the cells
(blastophthory).
The libido sexualis, or sexual desire in mankind is infinitely

stronger than is necessary for the reproduction of the race. Man has
no breeding season; he is always ready for sexual intercourse.
Although the number of women in the aggregate only slightly
exceeds that of men, the male has usually an instinctive inclination
to polygamy. Luther accurately estimated the normal requirements of
a healthy man in the prime of life at on the average two to three
sexual connections in each week; and yet this is far in excess of
what is necessary for the procreation of children in a monogamous
marriage. It is, moreover, well known that a man can even
considerably exceed the above number without injury to his health,
and there are women whose needs in this respect are actually
greater than those of men.
It therefore follows that the widespread artificial excitement of the
sexual desire from motives of sensuality is harmful from the
standpoint both of ethics and of social hygiene.
We cannot, it is true, be held responsible for a natural instinct
inherited from our ancestors. But we must seek to subdue this
instinct as far as possible, not to excite and stimulate it by artificial
means. Already there is more than enough purposeless, and
therefore ethically indifferent, sexual intercourse.
And yet Tolstoy is wrong in wishing to forbid this. As long as it
does no actual harm we must tolerate it, the more so because the
happiness of the individual and the cheerfulness with which he
labours are so often dependent upon the normal satisfaction of his
instincts.
Within the limits indicated above, the gratification of the sexual
instinct, whether in the case of man or woman, is in itself ethically
indifferent, provided it does not result in the procreation of children.
We have already dealt with the ethical value of procreation, which
depends upon the nature of the results expected. And we are
therefore bold enough to declare that every sexual connection which
does not injure either of the two persons who take part in it, or any
third person, and which, moreover, can do no injury to the child
which may be engendered by it, is in itself ethically indifferent, and
cannot therefore be immoral.
We have certainly imposed considerable modifications in this
sentence, for it is possible for a perfectly normal sexual connection
to do untold injury, especially to the woman and the child she bears;
so that an act which is in theory not immoral may become so in
practice, or may give rise to grave moral conflicts. This often
happens at the present time as the result of our prejudices,
established customs, and unjust laws.
From the standpoint of sexual ethics the ideal marriage is
undoubtedly a monogamous union, resting upon mutual and
enduring affection and loyalty, and consummated by the birth of
several children; a union in which the husband may be from six to
twelve years older than the wife, and both must be robust in mind
and body.
This ideal state of things is not as rare as our modern pessimists
would have us believe, but neither is it especially common.
Moreover, if this marriage is to reach that perfection which it can and
must attain, it must be completely free, that is to say, both parties
must be absolutely equal before the law, and no external compulsion
other than that of common obligations towards the children must
bind them to one another. To this end a complete separation of
property, and a just and proper valuation of every service performed
by the wife as well as the husband are of the first importance.
From the aforesaid it must by no means be inferred that every
person is to yield without restraint to his sexual desires.
Unfortunately this fundamentally false conception of free marriage
and free love is at the present time widespread, and it cannot be too
vigorously combated. In the first place, two persons are concerned in
the sexual act, and any exercise of constraint by one upon the other
is immoral and even criminal. The same holds true of every
seduction.
Moreover, the highest freedom of man lies in his mastery of self.
The only man who is truly free is the man who is able to control his
lower instincts. The compulsion which must be exercised in a
mutually happy sex relationship conformable to ethical principle
must, however, be no external legal compulsion, but an inward self-
repression. Fidelity in marriage must be a matter of mutual trust and
yet a matter of honour. The State and the laws cannot compel it, and
have never been able to do so; external constraint begets only
hypocrisy, strife, and treachery. On the other hand the State and the
law must, as time goes on, become more and more adapted to the
protection of the helpless offspring of sex unions.
Both parents, in proportion to their fitness and ability, must be
made responsible for the support of their children. It is in the highest
degree immoral to make a distinction between legitimate and
illegitimate children, and so to expose them and their mothers to
public disgrace because of the fulfilment of a natural function. Is it
not senseless, from the standpoint both of ethics and of law, to
declare the existence of a child, and therefore of a human being, to
be legal or illegal, or to speak of “natural children,” as if the others
were unnatural! In what bureaucratic brain can such an idea have
first arisen? It is only a remnant of a barbarous code of morals,
based upon the grossest prejudice. Antiquity, alas, justifies
everything—even crime!
Every woman who is healthy and strong should be proud of

becoming a mother. If sexual intercourse were frankly and naturally
treated as one of the most important acts in human life, the paternity
of the child would be easily ascertainable. A woman should not wait
until the birth of the child before speaking of it, but should promptly
make a formal declaration as to its parentage to the registrar of
births as soon as she becomes aware of her pregnancy. This would
be easily practicable if all girls received proper instruction regarding
the most important function of their lives. Instead of this, everything
is now concealed from them, and they are brought up in gross
ignorance of their sexual nature and duties.
If every pregnancy were at once legally recognised in this way,
and if the law would determine the responsibilities of both parents
towards their offspring, untrammelled by marriage laws and with the
well-being of society as its only aim, the most pressing need of our
time, from the standpoint of sexual ethics, would be satisfied. A
complete equality can only be attained by naming all children after
the mother. This is, moreover, the only rational and just system. It
was formerly the custom among many primitive peoples.
None of these reforms, however, need in any way debar the
formation of voluntary marriage contracts. Such contracts are,
indeed, distinctly advisable, for the voluntary resolve of two people to
remain faithful to one another, and to build up a permanent home for
their children, is at once the best, truest, and most natural foundation
of marriage.
But no one can foresee the future, and therefore simple facilities
for divorce must be provided in case it becomes intolerable or
inexpedient for the two persons to live together any longer. A divorce
must take place if one or both of the parties wish for it. The State and
the Law must only have the right to demand the fulfilment by the
parents of all obligations towards their children. Marriage contracts
for a fixed period are therefore as such not immoral. Such
agreements have even been recommended by the Christian
philosopher Charles Secrétan, in his book Le Droit de la Femme.
Sterile marriages, or other sex relationships, must be free. The law
has no concern with them as long as they do not involve injury to any
one’s property, health, or personal will. They are in themselves
ethically indifferent.
On the other hand, all sexual intercourse which is bought or sold,
such as marriage for money, the keeping of paid mistresses, and the
whole system of prostitution, is immoral, because it is corrupting and
devoid of love, and amounts simply to plunder by the aid of money.
Prostitution is a hotbed of sexual vices and abnormal practices. By
its means the sexual instinct is perverted and led astray into every
imaginable bypath, while women are degraded in the basest of all
slaveries.
Most repulsive of all, from the point of view of ethics, is the trade in
prostitutes known as the “white slave traffic,” with its criminal devices
for the enticement, intimidation, and seduction of young girls. The
traffic in waitresses for cafés and beer-gardens is often little better. It
is sad enough to reflect that these loathsome outgrowths of sexual
immorality often still enjoy the protection of the State, and that many
medical men defend their continuance under the pretext of hygiene.
It is just in this very respect that we see that social hygiene and
ethics are one and the same thing. Only the idiotic one-sidedness of
your specialist could declare such a monstrosity as State-established
prostitution to be hygienic. A system which makes for the mental and
physical ruin of the race cannot be hygienic, and the delusion that by
its aid men are protected from venereal disease is in direct conflict
with the actual facts.
Moreover, sexual intercourse which is bought and sold has no
relation to love. As a mode of gratifying the sex instinct it stands
even lower in the moral scale than the habit of self-abuse. And any
man who makes use of prostitution becomes an accomplice in
creating this miserable class of outcasts whom we speak of as
“unfortunates.” In short, whoremongery and prostitution are a social
cancer, and therefore in the highest degree immoral. They furnish an
instance of the manner in which money corrupts our whole
civilisation. This corrupting influence, with its robbery of one man by
another, makes itself felt in every department of life, and is exercised
by every form of private capital.
The climax of immorality in the cult of Mammon is reached,
however, by the capital employed in maintaining the two great evils
of alcohol and prostitution, both of which act as bloodsuckers upon
the vitality of the individual, the race, and all that is holiest in men.
These two forms of capital work hand in hand, fashioning the
goddess of love in the likeness of a lewd, sordid harlot, with the man
as at once her ravisher and her victim. They are also the worst
enemies of our descendants, whose procreation is often undertaken
in a moment of intoxication, and whose lives are exposed to the risk
of alcoholic degeneration or venereal disease!
These, therefore, are the chief foes of sexual morality: the struggle
for wealth (as exemplified in the domination of private capital) and
the use of alcohol. Let us combat both in the name of ethics. “In hoc
signo vincemus!”
The following will, I hope, make my meaning still clearer.

In sexual ethics many diseases and abnormalities play, of course,
a great part. First of all there are the venereal diseases, and
particularly syphilis and gonorrhœa, which often destroy family
happiness and endanger the offspring. It is too often forgotten that
chronic gonorrhœa can poison marriage, and that decay of the
spinal marrow (locomotor ataxia) and the so-called softening of the
brain (progressive or general paralysis) are nothing else than a very
late result of syphilis, appearing from ten to twenty years after
infection.
In a brief statistical discussion of the question, based upon
medical information, I have shown that seventy-five per cent of
venereal infections are acquired while in a state of alcoholic
excitement. In the vast majority of these cases the infection is
communicated by means of prostitution, which, as the result of the
incredibly numerous and varied sex relationships of the women,
serves simply as a vast manufactory of venereal diseases.
It is true that married women are often infected by their husbands
or lovers, but this is only a result of the previous visits of the latter to
houses of ill-fame. Hygiene and morals both suffer serious injury in
this way. Any one who is infected, and nevertheless has sexual
connection with a person not infected in the same way, commits a
basely immoral act, if not a crime. This is done, however, daily, when
the infection is concealed. Nay, more, the medical men who officially
visit and examine prostitutes are well aware that they can at most
only temporarily remedy a few of the worst symptoms, and that they
are powerless to cure the disease itself. In spite of this such women
are set at liberty once more to carry on their disastrous trade! And
very few prostitutes ever completely escape venereal infection.
These are the fruits of paid “love,” maintained chiefly by the
drinking habits of the present day. It is plain that the chief task of
sexual ethics must be the cleansing of this Augean stable. There are,
however, a host of other social evils of a similar kind, such as the
seduction and exploitation of waitresses, women factory workers,
and so forth. These abuses belong to the same domain and present
the same opportunities of infection.
The various perversions of the sexual instinct constitute another

prolific source of disaster. Most of these are hereditary, and therefore
inborn. We will only briefly mention sadism (the combination of acts
of cruelty and violence with sexual gratification), masochism (sexual
gratification combined with the passive endurance of similar cruelty
and violence), inverted sexual feeling (homosexuality), fetishism
(sexual attraction for inanimate objects), exhibitionism, sodomy, etc.
The unfortunate people who suffer from these perversions are
treated unjustly and, for the most part, far too harshly. Perverse
instincts which injure no one when carried into practice (fetishism, for
example), are ethically indifferent and harmless, in that their
possessors, generally speaking, do not multiply. It is, however,
immoral for such persons to marry. Any one who suffers from an
hereditary perversion of the sex instinct should avoid marriage and
all procreation of children.
But if the pervert can only gratify his instinct by injuring other
people, he must be regarded as a dangerous lunatic, and placed
under curative treatment. There must, however, be no question of
legal punishment. The foregoing treatment is above all necessary in
the case of sadists (who frequently commit murder) and in that of
persons of unsound mind who violate children. Homosexual persons
(i.e. men or women whose sexual inclination is for their own sex)
are, on the other hand, comparatively harmless as long as they
direct their attentions to adults, and provided there is no seduction or
use of compulsion. The same holds good in the case of other
perversions such as inclination for animals. Our laws are still entirely
at fault in these matters, and inflict punishment upon the basis of
ancient theological dogmas.
The case of perversions acquired by suggestion, evil example, or
frequent repetition is somewhat different. These latter are much
more readily curable.
Perverted sexual habits often arise from a craving for variety, or as
makeshifts adopted when the opportunity for normal sex intercourse
is denied. Our efforts must be directed towards removing these
causes by raising the general standard of social morals.
Religious morality has been the cause of untold mischief in this
matter of sexual perversions by representing as great sins and
crimes actions which are in reality the result of a diseased mental
state.
The habit of self-abuse is also extremely variable in its origin. It
arises usually as a makeshift, but often as the result of evil example.
It may also (although less frequently) be inherited, or originate from
nervous trouble, while in other cases it is prompted by mechanical
causes (phimosis, worms, or gymnastic exercises). There is no
greater blunder than that of exaggerating its importance by
representing it as a horrible and extremely dangerous vice. It must
be cured by pacification and soothing, by strengthening of the will,
and in some cases by providing the means of normal sexual
intercourse (not, however, by means of prostitution). This is the only
proper treatment of self-abuse, which is not as dangerous as is
commonly maintained. In this, as in all other cases, our conception
of sexual ethics will point out the right path.
Abnormalities of the brain or mind, especially constitutional

(hereditary) mental inferiorities, such as weakness of will-power,
moral idiocy (inherent lack of conscience), epilepsy, hysteria,
hypochondria, kleptomania, etc., together with all acquired mental
troubles, are the cause of innumerable sexual disorders and
perversions; of vices, crimes, and misdeeds of every description; of
rapine and seduction; of unhappy marriages, or rather hells upon
earth; and of the birth of countless doomed and wretched children.
Here we may see once again that ethics and social hygiene are at
one. Until now the theologians and the lawyers have treated these
mental conditions by denouncing them as deadly sins and
imprisoning the unhappy victims. This is disastrous to morality, to the
unfortunate persons themselves, and to society at large. Expert
mental treatment with a view to a fundamental cure is the first
necessity.
Here, again, alcohol and narcotics in general are the stone which
sets the whole avalanche in motion. The use of alcohol produces
mental inferiorities by its corrupting influence upon the cells
(blastophthory), and many people whose weakness of mind is
traceable to this cause cannot resist its use, and so become
dangerous inebriates.
Once more, it is the source and fountain of the evil that must be
stopped.
But there are other hereditary diseases and degeneracies of every
kind, not only of the brain, but of the whole body, such as the
disposition to tuberculosis, rickets, short-sightedness, and diseases
of the blood, all of which are related to sexual life and morals,
because they are all more or less injurious to the individual and to
society.
If persons suffering from such diseases have children at all they
must proceed with the greatest caution, and they should always be
instructed as to the hereditary nature of their maladies and the risk of
their transmission.
And now can we not hear the dictates of a truly human moral
code, based upon the facts that we have just considered?
It is true that we cannot change the present hereditary nature of
man, but it is none the less our duty, now that Science has revealed
this nature to us, to prepare for our posterity a greater degree of
happiness and a higher standard of social life than we now possess.
To this end we must first strive with all our might to destroy the all-
corrupting supremacy of private capital and wealth, with its
exploitation of human life and energy; and we must further combat
the use of all narcotic poisons, especially that of alcohol.
We must not rest until these two deadly monsters are overthrown.
In the sphere of sexual life we must endeavour to replace by truth
and justice the present-day hypocrisy which parades under the false
banner of “morality.” We must also restore to woman the same
natural and equal rights possessed by man.
Moreover, we must no longer be content to remain indifferent and
idle witnesses of the senseless and unthinking procreation of
countless wretched children, whose parents are diseased and
vicious, and whose lives are for the most part destined to be a curse
both to themselves and their fellow-men.
We must therefore recommend to all persons who are sickly or
infirm in body or mind, and especially to all suffering from hereditary
ailments, the use of means for the prevention or regulation of
conceptions,[D] so that they may not, out of pure stupidity and
ignorance, bring into the world creatures doomed to misery and
misfortune, and predisposed to disease, insanity, and crime.
[D] We refer, of course, to such preventive methods as are
completely harmless to the persons making use of them. Methods
for the prevention of conception, in general fulfil this condition.
We must endeavour in this way to bring about a vast and universal
sterilisation of all worthless, incapable or diseased people, without
attempting to prohibit in an ascetic and impracticable manner the
gratification of their normal sexual instinct and their desire for
affection.
The qualification for parentage must not be the possession of a
certain amount of money or property, but solely the social worth and
intrinsic hereditary qualities of the two individuals.
The multiplication of all who are healthy, capable, and ethically fit
must be encouraged as far as possible.
An excessive frequency of childbirths in the case of one woman
must be prevented and regulated by the use of the means
mentioned above.
In this way we shall carry out a true racial selection and prepare
the way for a better and happier Humanity. And so at last we shall
have brought our true sexual ethics into living being and reality.
Royal 8vo, 550 pp.
Just Ready.
Cloth. Price 21s. net.
THE SEXUAL QUESTION.

A SCIENTIFIC, PSYCHOLOGICAL, HYGIENIC, and
SOCIOLOGICAL STUDY for the CULTURED CLASSES.
By AUGUST FOREL, M.D., Ph.D., LL.D.

Formerly Professor of Psychiatry and Director of the Provincial
Lunatic Asylum, Zürich.
English adaptation by C. F. Marshall, M.D., F.R.C.S. (London).
With 23 Illustrations, 17 of which are printed in colours.
This book is the fruit of long experience and reflection. It has two
fundamental ideas—the study of nature, and the study of the
psychology of man in health and in disease.
“It is imperative that every man and woman shall know (1) the
complete facts of normal sexual life, i.e. the physical conditions of
reproduction; and (2) so much of sex pathology as is necessary in
order to avoid the many pitfalls existing round them. The highest
praise we can give Prof. Forel’s book is to say that it meets this
need. It is ‘a scientific, psychological, hygienic, and sociological
study’ of the sexual question.”—The New Age.
MARRIAGE AND DISEASE.

Cloth. Price 10s. 6d. net.
Being an Abridged Edition of “Health and Disease in Relation to
Marriage and the Married State.” (2 vols., 30s. net.)
By many Authors. Edited by Prof. H. SENATOR and Dr. S.
KAMINER.
Translated by J. DULBERG, M.D., J.P. (Manchester). Demy 8vo.
452 pp.
To give an idea of the scope of the work, it may be stated that it
contains chapters on such subjects as:—The Hygienic Significance
of Marriage, Congenital and Inherited Diseases and Predispositions
to Disease, Consanguinity and Marriage, Climate, Race and
Nationality in Relation to Marriage, Sexual Hygiene in Married Life,
Constitutional (Metabolic) Diseases, Diseases of the Nervous
System, Insanity, Alcoholism and Morphinism, Occupational Injuries,
Medico-Professional Secrecy, The Economic Importance of Sanitary
Conditions, &c. &c.
“The present book is an attempt to make available for general
consumption the gist of the larger work from which it is taken.... The
material contained in the book is most valuable, and a study of it
should be useful to those capable of appreciating it....”—The Lancet.
“It is a work which should be on the shelves of every public library
for the perusal of serious men and women, and especially young
men and women about to marry. It is a wonderful book.”—The
Sunday Chronicle.
FOOD AND HYGIENE.

A Scientific Book in simple language, dealing with such subjects
as the composition, character, and nutrient value of food, and
containing, as The British Medical Journal states, “a vast amount of
trustworthy information well arranged in a clear and plain style.” By
WILLIAM TIBBLES, M.D., L.R.C.P., M.O.H. Large crown 8vo., 684
pp., 8s. net.
HYGIENE OF THE LUNG IN HEALTH

AND DISEASE.
By Prof. Dr. L. von Schroetter. Trans. by H. W. Armit, M.R.C.S.
2s. net.
Hygiene is essentially a social science, and the Author has been
happy in his selection of the limits necessary for lay instruction.
MONISM? An Antidote to Prof.

Haeckel’s “The Riddle of the
Universe.”
By S. Ph. Marcus, M.D., 1s. net; by post 1s. 2d. Translated by R.
W. Felkin, M.D., &c.
London: REBMAN, LIMITED, 129 Shaftesbury

Avenue, W.C.
Medical, Scientific, & General Publishers. Catalogue & Descriptive
Circulars Post-free.

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Library of Congress Cataloging-in-Publication Data

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For information on all publications visit our

Publisher: Oliver Walter

Editor Biographies vii

1.01 Introduction: Volume I 1

1.03 Reversible Homolysis of Metal-Carbon Bonds 31

1.04 Very Low Oxidation States in Organometallic Chemistry 86

1.05 Very High Oxidation States in Organometallic Chemistry 109

1.06 Characterization Methods for Paramagnetic Organometallic Complexes 135

1.07 Computational Methods in Organometallic Chemistry 176

1.08 f-Element Organometallic Single-Molecule Magnets 211

1.09 Electrochemistry in Organometallic Chemistry 249

1.10 Organometallic Photosensitizers 284

1.11 Organometallic Chemistry of NHCs and Analogues 339

1.13 Redox-Active Ligands in Organometallic Chemistry 421

1.15 Introduction to the Organometallic Chemistry of Carbon Dioxide 474

1.16 Alkane s-Complexes 502

1.17 Dinitrogen Binding and Functionalization 521

1.18 Lewis Acid Participation in Organometallic Chemistry 555

1.19 Organometallic Chemistry on Oxide Surfaces 583

1.20 Separation Strategies in Organometallic Catalysis 609

1.21 Impurities in Organometallic Catalysis 635

Dermot O’Hare was born in Newry, Co Down. He studied at Balliol College,

Simon Aldridge is professor of chemistry at the University of Oxford and

Eszter Boros is associate professor of chemistry at Stony Brook University with

Scott R. Daly is associate professor of chemistry at the University of Iowa in

Lena J. Daumann is currently professor of bioinorganic and coordination

Patrick Holland performed his Ph.D. research in organometallic chemistry at UC

Ian Tonks is the Lloyd H. Reyerson professor at the University of Minneso-

Timothy H. Warren is the Rosenberg professor and chairperson in the Depart-

Matthew Asay Liang Deng

Vincent Lavallo Christopher GT Price

Comprehensive Organometallic Chemistry IV https://doi.org/10.1016/B978-0-12-820206-7.00166-9 1

2 Comprehensive Organometallic Chemistry IV https://doi.org/10.1016/B978-0-12-820206-7.00100-1

Before describing this effect, we need to review three simple ideas:

Carbon has sp-hybridization Experimental Calculated

H 2.592 2.528 0.320 104.2

Nb(V) 1.42 1.871 1.784 26.3

Determination of the A–X bond energy EA−X ¼ tcEc + ttEt (2)a

Ionic bond energy E i ¼ b  332 kcalÅ=mol (5)

says Mephistopheles in Goethe’s Faust.[B] Let us say often instead of

As a result of exaggerating the above-mentioned phenomena

“Es erben sich Gesetz und Rechte

[C] “Laws and statutes pass on in heritage, like an eternal

The libido sexualis, or sexual desire in mankind is infinitely

Every woman who is healthy and strong should be proud of

Ionic bond energy E i ¼ b 332 kcalÅ=mol (5)