Organic and Inorganic Chemistry

CYN-002
B. Tech I Yr. Courses

Dr. Dheeraj Kumar

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2
 Prof. Yadagiri
Dongari

Prof. R K Peddinti

Prof. Dheeraj
Kumar

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Coordination Chemistry

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5
 ORGANOMETALLIC CHEMISTRY
An area which bridges organic and inorganic chemistry
A branch of coordination chemistry where the complex has one or more metal-
carbon bonds

➢ The 18 electron rule

➢ Factors affecting M-C bond formation

➢ Metal carbonyls – synthesis, reactions and structures

➢ Transition metal-π alkene complexes-synthesis, reactions, bonding and

stability

➢ Applications of organometallic compounds in catalytic processes:

hydroformylation, hydrogenation, catalytic decarbonylation, olefin

metathesis and enantioselective hydrogenation of alkenes

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 Organometallic Compounds

Ferrocene
C always more electronegative compared to M

An "organometallic" compound is one in which there is a bonding interaction (ionic

or covalent, localized or delocalized) between one or more carbon atoms of an organic
group or molecule and a main group, transition, lanthanide, or actinide metal atom (or
atoms).
Following longstanding tradition, organic derivatives of the metalloids such as boron,
silicon, germanium, arsenic, and tellurium also are included in this definition.
It is also understood that the element to which carbon is bound is more
electropositive than carbon in organometallic chemistry.

• Traditional chemists do not agree for classifying metal cyanide

complexes as organometallic
• Many consider Wilkinson’s Catalyst as organometallic even
though such molecule lack the required M-C bond. Wilkinson’s Catalyst
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 Applications of Organometallic Compounds
Uses of organometallic compounds: Homogeneous catalyst in
industrial processes, Synthetic Precursors, Pharmaceuticals,
Agrochemicals, Flavors, Fragrances, Semiconductors and Ceramic
precursors.
Organometallic compounds provide a source of
nucleophilic carbon atoms which can react with
electrophilic carbon to form a new carbon-carbon
bond. This is very important for the synthesis of
complex molecules from simple starting materials.

❑ Olefin Metathesis

Nobel Prize – 2005 : Robert H.

Grubbs and Richard R. Schrock

❑ Metal catalysed cross coupling reactions

Nobel Prize – 2010 : Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for their work
in palladium-catalyzed coupling reactions in organic synthesis 8
 Zeise’s Salt - The first transition metal organometallic compound

Discovery 1827
Structure ~ 150 years later
W C Zeise, Danish
pharmacist, I789- I847 Potassium trichloro(ethylene)platinate(II)

Diethyl zinc - First  bonded Organometallic Compound

3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2

Frankland coined the term “Organometallic”

Prepared diethyl zinc while trying to make ethyl radicals.

Edward Frankland
1825-1899
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Hapto ligands and Sandwich compounds

The hapto symbol, , with a numerical superscript, provides a

topological description by indicating the number of carbon atoms at a
bonding distance to the metal

(5-C5H5)2Fe (6-C6H6)2Cr
G. Wilkinson E. O. Fischer
The Nobel Prize in Chemistry 1973 was awarded jointly to Ernst Otto Fischer and Geoffrey Wilkinson "for their
pioneering work, performed independently, on the chemistry of the organometallic, so called sandwich compounds

Bent Sandwich Half Sandwich Triple decker &

polycyclic

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 Bridging Ligands
• In coordination chemistry, a bridging ligand is a ligand that connects two or
more atoms, usually metal ions.

• In naming a complex wherein a single atom bridges two metals, the bridging
ligand is preceded by the Greek letter mu, μ, with a subscript number denoting
the number of metals bound to the bridging ligand. μ2 is often denoted simply
as μ.

• Ligands that are not bridging are called terminal ligands.

two chloride ligands are terminal cluster [Au6C(PPh3)6]2+

and two are μ2 bridging. μ3-chloride ligand features a μ6-carbide ligand

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 18 Electron Rule
When the metal achieves an outershell configurations of
ns2(n-1)d10np6, there will 18 electron in the valence orbitals
and a closed stable configuration.
This rule of thumb is called “18 electron rule”

According to this rule, in a complex, the sum of metal

valence electrons and the electrons donated by the ligands
is 18. It provides a closed and stable configuration, ns2(n-
1)d10np6.

e.g. Cr(CO)6, [Fe(CN)6]4−, Ni(CO)4, Mn2(CO)10, Co2(CO)8,

HMn(CO)5

All 18 electron organometallic compounds are generally Stable

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Methods of counting: Neutral atom method & Oxidation state method
Ligand Neutral Oxidation state Ligand Neutral Oxidation state
atom atom
Electron Formal Electron Formal
contribution charge contributi charge
on
Carbonyl (M–CO) 2 2 0 Halogen ( M–X) 1 2 –1
Phosphine (M–PR3) 2 2 0 Alkyl (M–R) 1 2 –1
Amine (M–NR3 ) 2 2 0 Aryl (M–Ar) 1 2 –1
Amide (M–NR2 ) 1 2 –1 acyl (M–C(O)–R 1 2 –1
Hydrogen (M–H) 1 2 –1 1-cyclopentadienyl 1 2 –1
Alkene (sidewise) 2- 2 2 0 1-allyl 1 2 –1
Alkyne (sidewise) 2- 2 2 0 3-allyl 3 4 –1
2-C60 2 2 0 5-cyclopentadienyl 5 6 –1
Nitrosyl bent 1 2 –1 6-benzene 6 6 0
Nitrosyl linear 3 2 +1 7-cycloheptatrienyl 7 6 +1
Carbene (M=CR2) 2 4 –2 Carbyne (MCR) 3 6 –3
Alkoxide (M–OR) 1 2 –1 Thiolate (M–SR) 1 2 –1
-CO (M–(CO)–M) 2 2 0 -H 1 2 –1
-alkyne 4 4 0 -X (M–X–M) 3 4 –1
X = halogen
-alkyl 1 2 –1 -amido 3 4 –1
(M–(NR2)–M
-phosphido 3 4 –1 -alkoxide 3 4 –1
(M–(PR2)–M (M–(OR)–M
Thiocarbonyl (M-CS) 2 2 0 Isocyanide (M-CNR) 2 2 0
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Neutral atom method: Metal is taken as in zero oxidation state for counting purpose

Oxidation state method: We first arrive at the oxidation state of the metal by
considering the number of anionic ligands present and overall charge of the complex

neutral atom oxidation state

method method
CO Ru 8 6 (Ru +2)
PPh3
Ru 3- allyl 3 4
2 PPh3 4 4
PPh3
CO 2 2
charge -1 not required
16 16
Me
N Fe 8 6 (Fe +2)
Me
Fe 2 5-Cp 10 12
18 18

Suggestion: Focus on one counting method till you are confident

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Easy way to remember ligand electron contribution for neutral atom counting method
Electron contribution
Neutral terminal : CO, PR3, NR3 2 electrons
Anionic terminal : X-, H-, R-, Ar-, R2N-, R2P-, RO- 1 electron
Hapto ligands : 2-C2R4 2-C2R2, 4-C2R2 ,1-allyl,
3-allyl, 4- Cb, 5-Cp, 6-C6H6
7-C7H7 8-C8H8 2-C60, 5-R5C60 same as hapticity
bridging neutral 2-CO, 3-CO 2 electrons
Bridging anionic 2-CH3, 2-H ( no lone pairs) 1 electron

Bridging anionic 2-Cl, , 2-OR, 2-PR2, 2-NR2 3 electrons

(with 1 lone pair)
3-Cl( 2 l.p) 5 electrons

Bridging alkyne 4 electrons

NO linear 3 electrons

NO bent ( l. p on nitrogen) 1 electron

Carbene M=C 2 electron

Carbyne MC 3 electron

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Valence Electrons Calculation

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18-electron Rule: Illustrative Examples

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 Q1) Consider the 18 electron rule as a guide and determine the value of n in
the following complexes.
(a) Na2Fe(CO)n
(b) MnBr(CO)n
(c) W(η6-C6H6)(CO)n
(d) Rh(η5-C5H5)(CO)n
(e) Cr(η3-C5H5)(CO)n(CH3)
(f) IrBr2(CO)n(CH3)

Q2)

Ans 1. (a) n = 4, (b) n = 5, (c) n = 3, (d) n = 2, (e) n = 4, (f) n = 1

Ans 2. (a) x = 2, (b) x = -3, (c) x = +1, (d) x = +1, (e) x = 0, (f) x = +1 19
Q3)

Q4)

Ans 3. A = Ni, B = Co, C = Mn

Ans 4. (a) NO is linear; (b) NO is bent, and (a) will have shorter M-N bond as three
electrons are donated to Ru. 20
 How to determine the total number of metal - metal bonds ?
Determine the total valence electrons (TVE) in the entire molecule (that is, the number of
valence electrons of the metal plus the number of electrons from each ligand and the
charge); say, it is A.

Subtract this number from n × 18 where n is the number of metals in the complex, that is, (n
× 18) – A; say, it is B.

(a) B divided by 2 gives the total number of M–M bonds in the complex.

(b) A divided by n gives the number of electrons per metal. If the number of electrons is 18, it
indicates that there is no M–M bond; if it is 17 electrons, it indicates that there is 1 M–M
bond; if it is 16 electrons, it indicates that there are 2 M–M bonds and so on.

Molecule TVE (18 × n) – A Total M–M Bonds per metal Basic geometry of
(A) (B) bonds (B/2) metal atoms

Fe3(CO)12 48 54 – 48 = 6 6/2 = 3 48/3 = 16; 2 Fe Fe

Fe
Co
Co4(CO)12 60 72 – 60 = 12 12/2 = 6 60/4 = 15; 3
Co Co

Co

[η5-CpMo(CO)2]2 30 36 – 30 = 6 6/2 = 3 30/2 = 15; 3 Mo≡Mo

(4-C4H4)2Fe2(CO)3 30 36 – 30 = 6 6/2 = 3 30/2 = 15; 3 Fe≡Fe

Fe2(CO)9 34 36 – 34 = 2 2/2 = 1 34/2 = 16; 1 Fe–Fe

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 A few worked out examples

Understanding metal –metal bond electron count become easier if you

compare and see how octet is attained by each Cl atom of Cl2 22
23
 METAL CARBONYLS
CO CO CO

CO OC CO
Ni OC Fe Cr
CO OC CO
OC CO
CO
CO CO

O
CO OC CO C CO
OC OC

OC Mn Mn CO OC Co Co CO
OC CO OC CO
CO OC C
O

CO
OC
CO CO
OC CO Ir
OC
CO Os CO OC CO
OC CO Ir Ir
OC CO
Os Os Ir CO
OC CO CO OC Heteroleptic Carbonyls
OC CO
CO CO

Homoleptic Carbonyls
• Carbonyl is one of the most important ligand in organometallic chemistry.
• Homoleptic Carbonyls (complexes containing only carbonyls as ligands)
• Coordination number around the metal normally remains six or lesser.
• 17 electron species such as Mn(CO)5, Co(CO)4 dimerize to gain 18 electrons.
• V(CO)6 does not dimerize. It exist as V(CO)6ˉ
• Most of the metal carbonyls have metal in very low oxidation state, sometime even zero and negative24
oxidation state.
 Why study metal carbonyls ?
• Simplest of organometallic compounds where M-C  bonding is well
understood. CO is one of the strongest  acceptor ligands.

• A range of metal carbonyls are used as catalysts in Chemical Industry

Hydroformylation Methanol to Acetic acid Process
Alkene to Aldehyde
R
(MONSANTO PROCESS)
C CH2
H MeOH + HI MeI + H2O

CO, CO H3C C I
HCo(CO)4 MeI
H2
[Rh(CO)2I2] O
R H2O
CH CH2 H3C C I H3C C OH
H HC O O
O
• Back bonding ( bonding) and variation in electronic properties of CO can
be monitored very efficiently by Infrared spectroscopy.

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 Molecular Orbital diagram of CO
*

Why does CO bind a metal through its less

electronegative carbon atom? What makes *

it a good  acceptor ? LUMO

✓ The highest occupied molecular orbital 2p

(HOMO) of CO is weakly antibonding 10.7 ev

(compared with the O atomic orbitals) HOMO
and is an MO which is carbon based.
✓ The * antibonding orbital which is the
lowest unoccupied molecular orbital
(LUMO) is also of comparatively lower 2p
energy which makes it possible to 15.9 ev

interact with metal t2g orbitals for 


bonding.
✓ There exists a strong back bonding of *
2s
metal electrons to the  * antibonding 19.5 ev

orbitals of CO.
Bond order = ½(Nb – Nab) = ½ (8-2) = 3  2s
32.4 ev
C CO O
CO is a very good σ donor as well as a good π acceptor. 26
 Orbital Overlap for  and  bonding in
metal carbonyls

First two electron donation of the lone pair on carbon into a vacant metal d-orbital
( donation). This electron donation makes metal more electron rich, and in order
to compensate for this increased electron density, a filled metal d orbital can
interact with empty π* orbital of the carbonyl ligand to relieve itself of the added
electron density (π back bonding).
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 Synergic Bonding in Metal Carbonyls

• The two components of this bonding are synergistic. The more sigma
donation by the carbonyl (or other sigma-donors on the metal center),
the stronger the pi-backbonding interaction.

• As the electron density on a metal center increases, more -back-

bonding to the CO ligand(s) takes place. This weakens the C-O bond by
pumping more electron density into the formally empty carbonyl *
orbital. This increases the M-CO bond strength making it more double-
bond-like, i.e., the resonance structure M=C=O assumes more
importance.
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 Extent of Backbonding in Metal Carbonyls

(No Back Bonding) (Full Back Bonding)

Real Metal carbonyls are in between these two structures (extremes).

• IR Spectroscopy (CO) and crystal structure (M-C bond length) will give
information will give idea about the structure.

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 Infrared Spectroscopy- A spectro-analytical tool in chemistry

Useful For Functional Group Determination

Infrared (IR) spectroscopy is one of the most common spectroscopic techniques used by organic
and inorganic chemists. Simply, it is the absorption measurement of different IR frequencies by a
compound positioned in the path of an IR beam. The main goal of IR spectroscopic analysis is to
determine the chemical functional groups in the sample. Functional groups are identified based
on vibrational modes of the groups such a stretching, bending etc. Different vibrational modes
absorb characteristic frequencies of IR radiation. An infrared spectrophotometer is an
instrument that passes infrared light through a molecule and produces a spectrum that contains
a plot of the amount of light transmitted on the vertical axis against the wavelength of infrared
radiation on the horizontal axis. Absorption of radiation lowers the percentage transmittance
value. 30 30
 Stretching Frequency in IR Spectroscopy

Stretching frequency (ν) is directly proportional to k ( depend on the bond strength).

The bonding in the carbonyl to the metal is highly sensitive to electronic
effects of the metal centre. This is usually monitored by IR Spectroscopy.

M C O M C O
 CO Higher  CO Lower
More back bonding

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✓ Co2(CO)8 has two isomers one with no bridging carbonyls
and other with two bridging carbonyl groups, both also being
18 electron species (How to differentiate?).
✓ As the C-O bond stretching frequency is quite sensitive to
small changes in the electronic environment, one can identify
these by IR spectral studies.
✓ The C-O stretching frequencies of terminal carbonyls come
in the range of 2125 - 1850 cm-1 while bridging carbonyl
stretching frequencies come in the range of approximately
1850 - 1700 cm-1.
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 Terminal versus bridging carbonyls
O
M O
C
C
C M
M M M
O
M
terminal bridging  2 bridging 
 3
CO 2120-1850 cm-1
1850-1700 cm-1 1730-1620 cm-1
Cp
CO Fe CO

OC CO
Cr OC Fe Cp
OC CO OC Fe
Cp
CO

2000 cm-1 2018, 1826 cm-1 Fe CO

Cp

termial bridging 1620 cm-1

Bridging CO groups can be regarded as having a double bond C=O group, as compared
to a terminal CO, which is more like a triple bond.
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Infrared Spectroscopy- Spectra of Metal Carbonyls

CO OC CO
OC

OC Mn Mn CO
The range in which
OC CO the band appears
CO OC
decides bridging or
terminal terminal .

The number of
bands is only
related to the
symmetry of the
O O
C
bridging molecule
OC C CO

OC Fe Fe CO
OC C CO
O

terminal

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 Factors which affect CO stretching frequencies
Variation in CO (cm–1) of the first row transition 1.Charge on the metal
metal carbonyls 2. Effect of other ligands
free CO
2143 As the electron density on a
Ni(CO)4 d8 metal centre increases,
2057
more -backbonding to the
Co(CO)4- Co2(CO)8 CO ligand(s) takes place.
1890
d8 2044(av, ter)
This weakens the C–O bond
[Fe(CO)4]2- Fe(CO)5
1815
d8 2030
further as more electron
density is pumped into the
[Mn(CO)4]3- Mn(CO)6 + Mn2(CO)10
1600,1790 d8 2098
d4 2013 (av) empty * anti-bonding
[Cr(CO)4]4- Cr(CO)6
carbonyl orbital. This
d4 increases the M–C bond
1462,1657 2000
V(CO)6¯ V(CO)6 order and reduces the
d4
1860 1976 C-O bond order. That is, the
Ti(CO)62- resonance structure M=C=O
d4
1747 becomes more dominant.

M C O M C O
 CO Higher  CO Lower
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More back bonding
 Effect of other ligands trans to CO
Effect of different Co-ligands on CO (cm-1) of Mo(CO)3L3

Complex  CO cm–1
(fac isomers)
Mo(CO)3(PF3)3 2090, 2055
CO
Mo(CO)3(PCl3)3 2040, 1991 More back bonding =
L CO
Mo Mo(CO)3[P(OMe)3]3 1977, 1888 More lowering of
L CO the C=O bond order =
Mo(CO)3(PPh3)3 1934, 1835
L More lower  CO
Mo(CO)3(NCCH3)3 1915, 1783 stretching frequency
Mo(CO)3(dien)* 1898, 1758
Mo(CO)3(Py)3 1888, 1746

The better the  donating capability of the other ligands on the metal, more electron
density given to the metal, more back bonding (electrons in the antibonding orbital of
CO) and lower the CO stretching frequency.
Based on CO IR stretching frequencies, the following ligands can be ranked from
best -acceptor to worst:

NO > CO > PF3 > RNC > PCl3 > P(OR)3 > PR3 > RCN > NH3 36
 Problems
1. The V-C bond length in V(CO)6- and V(CO)6 are 1.93 and 2.00 A°respectively.
Justify the bond lengths.
2. In a carbonyl complex with linear CO-M-CO group, how will CO change when a)
one CO is replaced by Et3N b) a positive charge is put on the complex c) a
negative charge is placed on the complex.
3. Arrange the following in the decreasing order of back donation
Cr(CO)6; [Ti(CO)6]-2 ; [Mn(CO)6]+ ; [Ir(CO)6]3+; [V(CO)6]-

4. Which of the following complexes will show a lower carbonyl stretching

frequency. Give reasons for your answer.

Cp Cp
Cl CO
Zr Zr
CO CO
Cp Cp
A B
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 Problems
Q1. Select the best choice in each of the following and briefly justify the reason for your choice
a) Complex with the shortest C-O bond
Ni(CO)4, [Co(CO)4]-, [Fe(CO)4]2-
b) Complex with the lowest C-O stretching frequency
Cr(CO)6 V(CO)6- Fe(CO)62+
Q2. Which one of the following complexes (a) and (b) will undergo ligand substitution faster with
PPh3? Why?
(a) V(CO)6 (b) [V(CO)6] ̶
Q3. The compound (ƞ5-C5H5)Co(CO)2 (A) upon UV irradiation, resulted in the evolution of a gas and
formation of a new compound, B. While the infrared spectrum of A showed absorptions around
1988 cm-1, the spectrum of B showed absorptions only at 1788 cm-1. Compounds A and B obey the
18 electron rule and both have cyclopentadienyl group in the ƞ5 mode. Draw the structure of
compounds B.
Q4. The compound Re(CO)5Br upon UV irradiation resulted in the evolution of an
equimolar amount of a colourless gas and the formation of a new stable complex X.
The infrared spectrum of compound X indicated the absence of metal-metal bond and
showed bands in the range of 2040-1965 cm-1. The starting material Re(CO)5Br also
showed bands in the same spectral range. Draw the structure of compound X.
Q5. In the given pair of complexes pick out the complex having lower energy CO stretching
frequency in its infrared spectrum. Rationalise your choice.
(a) Mo(CO)6 and Mo(CO)5PPh3 (b) Fe(CO)5 and Fe(CO)4Br2

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 Answers
1 : (a) Shortest CO bond Ni(CO)4 (b) Lowest CO stretching V(CO)6-.
2 : The mechanism of ligand substitution is different in both cases. V(CO)6 is a 17 e
system and it will prefer ligand substitution by an associative mechanism.
However [V(CO)6] ̶ is an 18 e coordinatively saturated complex and it will undergo
ligand exchange by a dissociative mechanism. Since CO is more tightly bound in
[V(CO)6] ̶ {higher back donation}, [V(CO)6] ̶ will be less reactive than V(CO)6.
3 : Infrared absorption of B indicates only
bridging carbonyls. To attain 18 electrons,
dimerization will take place with the
formation of a Co-Co double bond.
4 : The colourless gas has to be CO as bromine vapours are
coloured. Equimolar amount means one CO is released per
Re(CO)5Br; 2040-1965 cm-1, is the terminal carbonyl region.
Based on this and absence of metal-metal bonds, the structure
is one with bridging bromines
5 : (a) Mo(CO)5PPh3 will have lower CO since PPh3 is a poorer π acceptor ligand
than CO.
(b) Fe(CO)4Br2 [Fe2+ = 3d6]; Fe(CO)5 [Fe = 3d64s2]. Since the electron density on Fe0
is higher, back donation to CO will be more. Hence Fe(CO)5 will have lower CO .
39
NO > CO > PF3 > RNC > PCl3 > P(OR)3 > PR3 > RCN > NH3