Transition Metal Complexes withAcid Ligands

bondingOrganometallic Systems

Acid Ligands accept electrons from metal t2g orbitals (of symmetry) into
empty ligand t2g orbitals (e.g. P- and S- donors) or empty antibonding orbitals of
unsaturated ligand systems (e.g. carbonyls, alkenes, aromatics)

Acid Ligands form complexes with non-traditional geometries and unusual

metal oxidation states.

Acid Ligands stabilize metals in low oxidation states.

 Metal Carbonyls

O
O
C C O
O OC C
C
OC Cr CO Fe CO
Ni
OC OC OC CO
C C C
O O O

O O
C O C O O O
C C O C C
OC Mn Mn CO C
CO
Co Co
OC OC CO
C C OC C C
O O O O
 -Alkenes, Allyls and Aromatic Complexes

Alkene
H2C=CH2
C C
1,3-Butadiene
C4H6
M
M

Cyclobutadiene Cyclopentadienyl
C4H4
C5H5 (Cp)
M
M

C
Benzene
C6H6 -Allyl C C
C3H5
M M
MO Diagram for -Bonded Octahedral Metal Complex

t1u*

a1g*

4p
eg*
4s
o
3d t2g

6 ligand
eg orbitals

t1u
a1g

Metal ion, Mn+ [ML6]n+ Ligand, L

 *
C=O

M C O

Metal- d (t2g) *
Ligand - overlap

R
M P R
R

Metal- d (t2g) Ligand - d (t2g)

ML6 6 Ligand
ML6
Complex orbitals
Complex

t2g*

eg* eg * Ligand
(vacant)

t2g
(occupied)
t2gb
 ML6
ML6 6 Ligand
orbitals
Complex
Complex

t2 g*

eg * eg * Ligand
(vacant)

6 -donor ligands
(f illed)

t2 g
(occupied)

t2 gb

eg 18 electrons
f rom ligands
t 1u and metal
a1 g
 18-electron rule
O
O O C C
C O C
C CO
Cr 6 Co Co
OC Cr CO Cr(CO)6 CO
6 CO 12
OC C C
OC 18 O O
C
O
Co2(CO)8 Co 9
3 linear CO 6
O 2 bridging CO 2
C Co-Co 1
OC 18
Fe(CO)5 Fe 8
Fe CO 5 CO 10
18
OC O O
C C O C O
O C C
OC Mn Mn CO
O
C OC OC
Ni 10 C C
Ni(CO)4 O O
4 CO 8
Ni
18 Mn2(CO)10 Mn 7
OC CO
5 CO 10
C Mn-Mn 1
O
18
Bonding in Transition Metal Alkene Complexes. [PtCl3(C2H4)]-

Metal ( Alkene (
Metal (t2g) Alkene (

H H
H H

C C

M M
C C

H H
H H
 O
C
OC CO
Ru

Ru 8 Ru 8
3 linear CO 6
2 alkene 4 Ru C8H8 4
18 3 CO 6
OC CO
18
C
Ru O
OC CO
C Ru(C8H8)(CO)3
O
 C
O H
W 6
C5H5 3 Ti 4
W Ti H
5-C5H5 5 5-C5H5 10
CO
2 CO 4 C5H5 2
18 16

W(C5H5)(5-C5H5)(CO)2 Ti(C5H5)2(5-C5H5)2
 H H Tropylium ion

Fe 8 6
Mo
C7H8 4 C7H7+ 6
3 CO 6 3 CO 6
18 Mo 18
Fe
OC CO
OC CO
C
C O
O
[Mo(C7H7)(CO)3]+

Fe( C7H8)(CO)3
 16/18-electron counts for
d-block organometallic compounds

Usually less Usually 16 or 18

than 18 electrons 18 electrons electrons

Sc Ti V Cr Mn Fe Co Ni
Y Zr Nb Mo Tc Ru Rh Pd
La Hf Ta W Re Os Ir Pt
 Metal Clusters
A characteristic of metal atoms bonded to organic ligands, especially CO, is their
tendency to covalently bond to other metal atoms, giving rise to metal-metal
bonded cluster compounds.
There appears to be no limit to the size of metal clusters. They can contain
numbers of metal atoms ranging from 2 or 3 to several dozen. e.g. Ru3(CO)12,
Ir4(CO)12, Pt38(CO)44

Metal clusters may contain single, double, triple or quadruple bonds between
metal atoms. Metal clusters can encapsulate non-metallic atoms such as C or N
(carbide or nitride clusters) in which the non metal may be bonded to 5 or 6 metal
atoms, e.g. [Fe6C(CO)16]2-.

They may or may not contain bridging CO ligands (e.g. CO, 3-CO). As
negative charge accumulates in series of isoelectronic clusters, more carbonyls
are found to be bridging. Bridging tendency decreases down a group.
The metallic skeleton is generally derived from polyhedra that may resemble bulk
metals in structure. e.g. [Rh13(CO)24H3]2- and Pt3S(CO)44 resemble hexagonal close
packed and body centered cubic metallic lattices, respectively, with "rounded
surfaces".
Clusters can exhibit properties characteristic of heterogeneous catalytic metal
surfaces
-acid ligand clusters show structural analogies to boron clusters
 Rationalization of Cluster Structures

Polyhedral Skeletal Electron Pair Theory

 Bonding in Boranes and Metal Clusters
Parallels between main group (p-block) and organometallic chemistry, boranes
and transition metal clusters

Boranes

Classification of boranes:

closo- (cage-like) boranes BnHn2-. Closed polyhedra with n corners and all triangular
faces (i.e. deltahedra). Each corner is occupied by a BH group (e.g. B6H62- with Oh
symmetry, B12H122- with icosohedral symmetry).

nido- boranes. Polyhedra with one corner removed from a closo framework (nest-like).
e.g. B5H9 (from B6H62- - BH + 2H+ + 2H)
B10H14 (from B11H112- - BH + 2H+ + 2H)

arachno- boranes. Polyhedra with two corners removed. (spider-like).

e.g. B4H10 (from B6H62- - 2B + 2H+ + 2H).

hypho- boranes. Polyhedra with three corners removed. (net-like)

e.g. B5H12 (from B8H82- - 3B + 2H+ + 2H).
 Bonding in boranes

2s 2p

B (2s)22p1 + H (1s1) = 4 e- for BH unit

B 1 sp hybrid for external B-H bond

sp sp 2p 2p
1 sp hybrid for internal cluster bonding

n internal 1 bonding M.O.

p-orbitals for
External surface cluster + n-1 antibonding M.O.
B-H bonding bonding
p
2n p-orbitals n bonding
p
+ n antibonding M.O.
Cluster
H sp
B sp bonding
(n + 1)
bonding Cluster has n + 1 bonding M.O.'s
M.O.'s
(2n + 2 cluster framework electrons)
containing

2n+2
electrons
 Wade's "2n + 2" rule for electron- deficient borane clusters

Valence electrons - external (B-H) electrons = cluster framework electrons

Total valence External Cluster

electrons B-H electrons framework
electrons

closo- B6H62- 26 12 14 2n + 2

nido- B5H9 24 10 14 2n + 4

arachno- B4H10 22 8 14 2n + 6

closo- B7H72- 30 14 16 2n + 2

arachno- B5H11 26 10 16 2n + 6

closo- B12H122- 50 24 26 2n + 2

nido- B11H132- 48 22 26 2n + 4
 Delocalized Metal Cluster Electrons
V = 14n + 2
______________________________________________________

Total valence electrons (V) - external cluster electrons (n x 2)

- metal core electrons ( n x 10)

= cluster framework electrons (2n + (2))

__________________________________________________________ ______________________________________________________

V = 14 n + (2)
 Total valence -(external valence = cluster framework or
electrons (V) electrons and core electrons
electrons) V = 14n + 2
-12n 2n + 2

Os5(CO)16 72 -12 x 5 12 = 2n + 2 14n + 2

trigonal closo
bipyramidal

Os3(CO)12 48 -12 x 3 12 = 2n + 6 14n + 6

planar triangular Arachno

Os6(CO)18 84 -12 x 6 12 = 2n + 0 14n

capped trigonal capped closo
bipyramid

5Cp)RhFe3(CO)11 60 -12 x 4 12 = 2n + 4 14n + 4

nido

Re4(CO)162- 62 -12 x 4 14 = 2n + 6 14n + 6

arachno

Fe5C(CO)15 74 -12 x 5 14 = 2n + 4 14n + 4

nido
Polyhedral Fragments Isolobal Principle
 Fragment Donor Electrons
O
C
Co(CO)3 OC Co Co(9) + 3 CO(2) = 15 -12 = 3e-

C
O

O
C
Fe(8) + 3 CO(2) = 14 -12 = 2e-
Fe(CO)3 OC Fe
C
O

Fe(8) + Cp(5) = 13 - 12 = 1e-

Fe(C5H5) Fe

Ni(C5H5) Ni Ni(10) + Cp(5) = 15 - 12 = 3e-

B-H H B B(3) + H(1) = 4 - 2 = 2e-

C(4) + H(1) = 5 - 2 = 2e-

C-H H C

H
C(4) + 2 H(1) = 6 - 4 = 2e-
CH2 C
H

N N N(5) = 5 - 2 = 3e-

O O O(6) = 6 - 4 = 2e-
 Isolobal Fragments

CH2 Fe(CO)3
B-H O
H O
C
H B C
H O
OC Fe
C
O

Ni(C5H5) N

Ni N
The number of electrons provided for cluster
bonding by selected fragments

Cluster fragments Cr, Mo, W Mn, Tc, Re Fe, Ru, Os Co, Rh, Ir

M(CO)2 -2 -1 0 1

M(CO)3 0 1 2 3

M(CO)4 2 3 4 5

M(-C5H5) -1 0 1 2

M(-C6H6) 0 1 2 3

M(CO)2(PR3) 0 1 2 3