Chapter 1.

General properties of organometallic

complexes
Outline
1.
2.
3.
4.
5.
6.
7.

Review on coordination chemistry

The 18-electron rule
Limitations of 18-electron rule
Oxidation number
Coordination number and geometry
Effect of complexation
Differences between metals

References
1. The Organometallic Chemistry of the Transition Metals, Robert H. Crabtree,
3rd Edition, 2001, Chapter 1-2.
2. Organotransition Metal Chemistry, Akio Yamamoto, 1986. Chapter 1-4.
3. Organometallic Chemistry, G. O. Spessard, G. L. G. L. Miessler, PrenticeHall: New Jersey, 1997, Chapter 1 3.

1. Review on coordination chemistry

Complexes or coordination compounds are compounds composed
of a metal and ligands which donate electrons to the metal, e.g.
NH
.. 3
H3N:
H3N:

Co
..
NH3

3+

3+
:NH3
:NH3

NH3
or

H3 N
H3N

Co

NH3
NH3

NH3

Ligands: a molecule or ion that has at least one electron pair that can be
donated.

Theelectronpaircanbe:lonepair,bondingelectronpair,or
bondingelectronpair.

Classification of ligands
A). Based on nature of the donating electron pairs, ligands may be
classified as Lone pair donor, -bonding electron pair donors, -bonding
electron pair donors.

lone pairs, e.g.

H3N:

H3N:

..
..
H2O: H2O:

bonding e- pairs, e.g.

M
bonding e- pairs, e.g.

H H
M

M
H

SiR3
M

1) Lone pair donors

:L

H3N:

..
..
NH2-CH2 -CH2-NH2 (en)

In terms of bonding:

M
empty

:CO :PR3

..
R-O.. :

..
Cl :
..

L or M

M L

filled

MO description of Metal-Ligand interactions

Antibonding

Note:

L ligand

Ligands that donate

electron pairs to form M-L
bond are also called

M
L ligand

L ligand
Bonding

donors.

Some lone pair donor ligands may have orbitals to

form M-L bonds. ===> donor, acceptor.

e.g. OR.. :
R-O
..

OR-

(a)

(a)

.. :
R-O
..

OR- or M

empty filled

R-O

(b)

R-O

Note: although
ligands such as ORcan form bond
with a metal, we
usually don't indicate
such interaction in
writing the
structures.

OROR-

OR

OR

OR

Ligands that donate electrons to metal to form bond are called donor
How many bonds can an OR form with a transition metal ion?

CO is not only a donor, but also a acceptor.

:C O:

(a)
C O:

+ C O:

(b)

C O:

C O:

empty
accept e- to form bond (dp back bonding)
Ligands that accepting electrons from metal to form p bond are called acceptor.

How many bonds can a CO form with a transition metal ion?

:C O:

(a)
C O:

+ C O:

C O:

C O:

empty

+ C O:

C O:

empty

M C O

M C O

Can CO function as a donor?

M C O

Types of lone pair donor ligands

lone pair
donor

strong
acceptor

weak
bonding

CO, PF3

NH3, HCH3-

strong
donor
Cl-, OR-

Evidences for d-p interactions.

* Take M-CO complexes as an example for accepter
2.38

1.99

a)

OC
OC
b)

Mo

2149 cm-1

CH3

CO

H3 B C

2
C

O 3

(anti-bonding)

IR, (CO)
:C

2178 cm-1

CO CO
OC Cr
CO
OC
CO

2000 cm-1

Explanation?
The lone pair on C atom has a little
anti-bonding character.

:C

M
M

:C

C
C

M C

+
M

*Take M-OR complexes as an example for donor.

t-Bu
t-Bu O O
Mo

t-Bu
O O t-Bu
120o
Mo

O O
O
O

Tp

180o
O
Nb
O

Tp
Tp = trypticyl

In H2O, O atom has sp3 hybridization, leading to the A-O-B angle

being about 104.5. However, in the above two complexes the
angles are 120 and 180, respectively. Why ?

2). -bonding electron pair donors

C O

H2C

CH2
M

HC

CH
M

How can these ligands interact with M ?

Take CH2=CH2 as an example.
H H

H
H H

C
M

M
H

C
M

1. e- from (C 2H4) ---> (M) 2. e- from d(M) --->(C 2H4)

Is CH2=CH2 a donor or a acceptor?

Hapticity of ligands:
A ligand may have more than one way to bond to a metal center, e.g.
CH2

CH

CH2

H
H

H
(Cp)

H M

M H

H
H

or

H
H

In describing the number of atoms (n) attached to a metal, a short

hand n is used. e.g.
M
M
1

( -C3H5)M

H
H

(-H2)M

CH2

Ag+

CH2

(-C2H4)M

(-C6H6)M

(-C6H6)Ag+

(-C6H6)M

Exercise. Give the hapticity of ligands in following complex

Fe(CO)3

Ru

CH3

MeO

Fe(CO)3

Notes: Notation of bridging ligand: n

Cl

Cl
M

M
2-Cl

H
M

C
M

3-Cl

H
B

2-OR

H
H
M

H
M

B
H
4

M
H

H
M

3-CO

H
B

H
M

B
H
M

H H
M

3). -bonding electron pair donors

Relatively fewer stable complexes are
known.
Typical examples:

-H2

OC
OC

PR3

-H-SiR3

PR3
CO
H
W
H

SiR3

Mn H
OC
OC R3Si
Cl

agostic C-H

H
C

or M

H
C

Me2P
Me2P

Ti
Cl

CH2
Cl

CH2

How can these ligands interact with M? Take H2 as an example.

H

M
-bonding

M
-bonding

Further Notes:
* Relative basicity of electron pairs:
lone pairs > bonding electron pairs > bonding electron pairs
* Therefore usual order of binding ability:
lone pair donor > bonding electron pair donor > bonding electron pair donor.
Consequence:
CH2
:PR3
CH2
CH2
H
M PR3
M
M
CH2
H
H
CH2
H

CH2

* Some ligands have several types of electron pairs.

The types of e- pairs to be used to bind metal will depend on
metals. e.g.

R
H

C O

C
R
H
low oxidation state M

O
C H
R

high oxidation state M

B) based on the nature of bonding interaction, ligands may be

classified as soft or hard.
Hard ligands: have low polarizability, especially those containing
period 2 donor atoms N, O, F, e.g. O2H, NH3, FSoft ligands: have high polarizability, they include:
a). Those with period three or subsequent donor atoms,
e.g. Cl, Br, S, P.
b). -acceptors, e.g. CO, CS (carbon sulfide), H2, CN- (cyanide)
c). Those containing p-electrons, e.g.
C

Importance of the concepts of soft and hard ligands:

* Hard ligands tend to form stable complexes with hard metal ions,
(usually those at high oxidation state, e.g. Al3+, Fe3+, Cu2+, Ti4+, Pt(IV)).
* Soft ligands tend to form stable complexes with soft metal ions,
(usually those at low oxidation state, e.g. Mn(I), Co(I), Fe(II), Pt(II),
Pt(0) .......)
Examples:
AlF63-, Ti(OR)4 are very stable complexes, but Pt(0)--F, Pt(0)--OR,
W(0)--F are very rare.
Cl
Cl

Pt

Pt(IV)

Cl

stable

very rare

Exercise. explain the following facts based on the concept of Soft-Hard

Acid-Base.
1) W(CO)6 is air stable, but W(NH3)6 has never been observed.

2).

NH2
II

(NH3)5Os

2+
NH2

-e

3+

(NH3)5OsIII
slow
(NH3)5OsIII

NH2

3+

3). Low oxidation state complexes (most organometallic compounds) are

often air-sensitive, but are rarely water sensitive.

Further notes on ligands

General presentation of Ligands:
L: form coordination bond with a metal (e.g., CO, PR3)
X: form covalent bond with a metal (i.e., H, Cl, CH3)

MXL5

MX2(L2)

MXL(LX)

Types of ligand coordination:

Terminal: Ligand is bound to only one metal center (L-M or X-M)
Bridging (): Ligand is attached to different metal centers
Hapticity (): Ligand attached to a metal center through more than one
atoms
H
H
M

B
H

H
H M

M
3

B
H

M
4

Further notes on ligands

Chelation: Ligand attached through more than one atom usually separated
by one or more atoms. Chelating ligands are sometimes classified as being
bidentate (2 points of attachment), tridentate (three points of attachment), or
tetradentate (4 points of attachment).

Kappa convention (): The kappa convention is sometimes used to

indicate the coordinating atoms of a polydentate ligand.

2. The 18 electron rule

1) Thermodynamically stable transition metal organometallic
compounds are formed when the sum of the metal d electrons plus
the electrons supplied by the ligands equals 18.
In this way, the metal formally attains the electronic
configuration of the next noble gas.
The 18 electron rule = 18 VE rule = inert gas rule = effective
atomic number rule (EAN rule). e.g.
CO
CO

OC

OC
Fe

Ni
OC

CO

OC

CO
CO

OC
OC

CO

10 + 4x2 = 18

Cr

CO
CO

8 + 5x2 = 18

CO

6 + 6x2 = 18

Saturated complexes: 18 VE complexes

Unsaturated complexes: <18 VE complexes

Why 18?

2) Ways to count valence electrons (VE)

# VE = valence e- of M (or Mn+) + e- from ligands
Two Models: covalent model and ionic model
Covalent model : Both M and L are considered as neutral
# VE = valence e- of M + e- from ligands + charge
e.g.

Fe

2C5H5

2 x 5e

Fe

8e
18e

CO
OC Cr CO
OC
CO

For TM, valence e- of M = group number

5 CO
H
Cr
1-

5 x2e
1e
6e
1e
18e

Ionic model : Metal complexes are formed from Mn+ + L +

X# VE = valence e- of Mn+ + e- from ligands

2 C5H5Fe

Fe2+

2 x 6e
6e
18e

5 CO

H
CO
OC
OC

Cr
CO

CO

HCr

5 x 2e
2e
6e
18e

Exercise:
Determine the valence electron count of the following complexes.
CO
OC

Mn

CO

OC
CO

OC
OC

CO
CO
Mn

OC

Mn

CO

CO OC CO

O
C

OC
OC

CO
CO

Fe

O
C

CO

Fe
C
O

CO

CO

Cl

Cl
Cl

Fe(CO)3

Fe(CO)3

Cl

CH3

CH3

Rh

Rh

Rh

Rh

MeO

Fe(CO3

Cr

Ru

Mn
OC

CO
OC

Fe
OC

OC

CO
CO

CO
Rh

Rh

OC

Ph2
P
Ir(CO)2(PPh3)

(CO)3(PPh3)Fe

O
N
Co

Co
N
O

Do the following complexes follow the 18e rule?

ReH7(PPh3)2

+
Rh

CO
OC
OC

H
H
H

CO

Cr
CO
CO

Cr
OC

CO

CO
CO

H
R3P Ru
R3P

PR3
H
B

H
H

R3P

Ru

R3P

PR3
H
B

NMe3
H

Additional exercise
PPh3

Ir
OC

CO

BPh3

Ir
OC

CO

N
Ir
OC

CO

3. Limitations of the 18 electron rule

Most OMC follow 18e rule. But there are many stable compounds that
do not have 18 valence electrons. e.g.
WMe6 (12e)

Pt(PCy3)2 (14e)

[Cu(NH3)6]2+ (21e)

RhCl(PPh3)3 (16e)

Question: When the 18e rule works?

Some general observations:
1). Many main group complexes do not follow 18e rule:
e.g. ZnMe2 (14e),
IF7

(24e),

Cp2Be (12e),
SbF6-

(22e)

2). F-block metals do not follow 18e rule. e.g.

Lu Me

U: 7s25f36d1

Lu: 6s24f146d1

2x8+6 = 22e

2x5+1+17 = 28e

Why? because electrons can go to (n-2)f orbitals)

3). Transition metal complexes ===> three classes

Class

number of valence electrons

18e rule

....16, 17, 18, 19, 20

not obey

II

....16, 17, 18

not obey

III

18

obey

Class I

n(VE) = 18 ~ 22
n(d)

n(VE)

TiF62-

12

VCl62-

13

V(C2O4)33-

14

Cr(NCS)63-

15

Mn(CN)63-

16

Fe(C2O4)33-

17

Co(NH3)63+

18

Co(H2O)62+

19

Ni(en)32+

20

Cu(NH3)62+

21

Zn(en)32+

10

22

Class II: 4d and 5d metals with weak-field ligands

ZrF62-

n(VE) 18
n(d)
0

n(VE)
12

WCl6

12

WCl6-

13

WCl6 2-

14

TcF62-

15

OsCl62-

16

PtF6

16

PtF6-

17

PtF62-

18

PtCl42-

16

Class II

Metals in relatively
High oxidation state

Class III: Complexes with good acceptors

Class III

n(VE) = 18
n(d)

n(VE)

V(CO)6-

18

CpMn(CO)3

18

Fe(CN)64-

18

Fe(CO)42-

10

18

MO levels in the absence of acceptors.

Explanation:
L
Take Oh

L
L

L
L

t1u*
as an example

np

* If is small, eg* can be

occupied. ( < pairing energy)
===>
eg* (antibonding):
t2g (nonbonding):
a1g, t1u, eg (bonding):
Total e-:
Minimum # of e-:
Maximum # of e-:

0 - 4e
0 6e
12e

a1g*
eg *

ns
(n-1)d
metal
orbitals

(a1g+eg+t1u)

t2g
Ligand
orbitals
(a1g+eg+t1u)

3d metal complexes with weak field ligands e.g. H2O, NH3 and
Cl- belong to this class (class I).

MO levels in the absence of acceptors.

t1u*

* If is large, eg* can be

occupied. ( > pairing energy)
===>
eg* (antibonding):
t2g (nonbonding):
a1g, t1u, eg (bonding):
Total e-:
Minimum # of e-:
Maximum # of e-:

np
0e
0 6e
12e

a1g*
eg*

ns
(n-1)d
metal
orbitals

(a1g+eg+t1u)

t2g
Ligand
orbitals
(a1g+eg+t1u)

Complexes of 4d and 5d metals in high oxidation state belong to

this class (class II).

* In the presence of -acceptors:

np

t1u*

t1u*

a1g*

a1g*

np

eg*
ns
(n-1)d
metal
orbitals

(a1g+eg+t1u)

t2g
Ligand
orbitals
(a1g+eg+t1u)

ns
(n-1)d

t2g*

eg*

t2g

metal
orbitals

*
(a1g+eg+t1u)
Ligand
orbitals

a1g+eg+t1u

is large. t2g are bonding MOs, and prefer to be occupied.

===> eg* (strongly antibonding):
t2g (bonding):
a1g, t1u, eg (bonding):
===>Total e:

0e
6e
12 e

Since
organometallic
compounds
usually have acceptors, is
large and t2g are
bonding MOs.
They usually have
18e valence
electrons (class
III).

Note, just like the octet rule, the 18-electron rule is not an
absolute requirement. There are many exceptions.
Common exceptions to the 18 electron rule:
z
d8 metals:
The d8 metals (groups 8 - 11) have a
tendency to form square-planar 16
electron complexes.

2eu
a2u
eu

This tendency is weakest for group 8

(Fe(0), Ru(0), and Os(0)) and is very
strong for groups 10 and 11 (Pd(II),
Au(III)).

L
L

L
L

1a2u
2b1g

a1g
s
eg

3a1g

2a1g
d
1eg+1b2g
b2g

b1g

1b1g

a1g

1eu
1a1g

Because 2b1g orbital is very high-lying and is usually empty

d0 metals: The high-valent d0 complexes often have lower

electron counts than 18.

Complexes with bulky ligands: Sterically demanding

ligands will often result in lower than expected electron
counts.

> 18 electron complexes: Complexes with formally 19 or 20

electrons are known, but they are usually unstable, or
adopt alternate configurations.

The 18 Electron Rule Is Empirically Justified

The rule is
particularly useful for
Groups 6-8

16 e- Compounds

14 e- Compounds

4. Oxidation number of metals and d electron

count
The oxidation state of a metal in a complex is simply the charge that
the metal would have on the ionic model.

d electron count: # of d electrons in the valence shell

= group # - oxidation state.

e.g. What is the oxidation number of metals in the following

complexes?
WMe6

OC
OC

PPh3
Cl
Os
Cl
PPh3

H
H
R3P

PR3
Fe
H
H
PR3

4. Oxidation number of metals and d electron

count
The oxidation state of a metal in a complex is simply the charge that
the metal would have on the ionic model.

d electron count: # of d electrons in the valence shell

= group # - oxidation state.

e.g. What is the oxidation number of metals in the following

complexes?
WMe6

OC
OC

PPh3
Cl
Os
Cl
PPh3

W(VI)

Os(II)

H
H
R3P

PR3
Fe
H
H
PR3
Fe(II)

Problems with O. S. :
a) Ambiguous oxidation states
(Ph3P)2Pt

(Ph3P)2Pt

Pt(0)

Pt(II)

PPh3
OC
OC

Os

PPh3
CH2
O

PPh3

Fe(0)

Os

CH2
O

PPh3
Os(II)

Os(0)

Fe(CO)3

OC
OC

or

Fe(CO)3
Fe(II)

Convention used in this course.

or

Fe(CO)3
Fe(IV)

b) charge density and formal oxidation states

Consider complexes W(CO)6 and WH6(PMe3)3.
Which one would you expect to have a higher positive charge on
W?
W(CO)6 W(0):
W CO backdonation
WH6(PMe3)3

W(VI): actually more e-rich

Another example

There is no strict correlation between charge density and

formal oxidation states! Oxidation states in organometallic complexes
are merely formalisms that may bear little resemblance to the actual positive
charge on the metal.

Any Uses of formal oxidation states?

Oxidation number usually can not be higher than
group member !
==> predict if a compound/intermediate is possible
==> Help to formulate the structure of a compound.
e.g.
(1) Are the following species possible?
WMe6 TiMe6
VH7(PMe3)2

(2) WH6(PMe3)3 + HBF4 ------> [WH7(PMe3)3] BF4

+
Which of the following is unlikely the structure for
+ 7(PMe3)3] ?
H [WH
H

H
P

H
H

P P

(a)

H
W

H
P

H
H

P P

(b)

H
W

H
P

H
H

P P

(c)

5. Coordination number (C.N.) and geometry

a) It is easy to define C.N. for complexes with lone pair donors.
* Monodentate ligand L :
C.N. = # of L present = # of atoms bound to metal
= # of electron pairs involved in M-L bonds.
e.g.

Cl
H3N
H3N

Co

Cl
NH3

ReH92-

NH3
six-coordinated

9-coordinated

Polydentate ligands:
C.N. = # of atoms bound to metal
= # of electron pairs involved in M-L bonds.
# of L present

Ph2
P

CH3
Co

P
Ph2

Cl

4-coordinated

Ph2P
H
Ph3P

Ir

PPh3

Cl
6-coordinated

b) For Organometallic compounds, it is difficult to define C.N. e.g.

Fe

Fe

CO
CO

OC
# of L

C.N. = 1

C.N. = 1 + 3

Fe

Fe
OC

# of M-L

C.N. = 5

C.N. = 3

CO

C.N. = 4 + 3

Fe

Fe

# of e pairs in M-L bond

CO

OC
2

CO

CO

C.N. = 2 + 3

Convention used in this course.

We normally adopt the e- pairs in M-L bonds as # of C. N..

Exercise. What is the coordination number of following complexes?

OC

Fe
OC

+
M

Further notes on coordination numbers:

a). For TM, C.N. 9 , why?
TM has 9 valence orbitals ((n-1)d, ns, np).

b). dn <==> C.N. and geometry

dn

C.N.

d6

prefer

octahedral

d8

prefer

square planar

prefer

tetrahedral

d0, and d10

geometrical structure

c). Each C.N. is associated with one or more

geometries.

Some common coordination numbers and geometries

2

linear

Mn(CH2SiMe3)2

trigonal

Al(mesityl)3

T-shape

Rh(PPh3)3+

square planar

RhCl(CO)(PPh3)2

tetrahedron

Ni(CO)4

Prefered dn
d0,, d5, d10

d8
d8

d0,, d5, d10

Trigonal
bipyramidal

square
pyramidal

Fe(CO)5

Co(CNPh)52+

d8,, d6

d6,, d7

(benzonitrile)

Octahedron
trigonal
prism

Mo(CO)6
WMe6

d6,, d3

d0

6. Effect of complexation
M-L:
Complexation of L on M may cause:
* the change of electron density distribution
on L
* new reactivity of L: unreactive ==> reactive
a. Change the electron density on L.
donation will reduce electron-density of L.
-accepting will increase electron-density of L.

Examples:

H2C

CH2

+ Nu-

N. R.

but,

OC
OC

Fe +

+ ROC
OC

Fe
R

Complexation reduce electron-density of olefin

Another example,
H

H
H

HE
+

-H

E
H

NuN. R.
+

but,

H
H

NaBH4

Mn
OC CO

CO

E+

(H-)

Mn
OC

CO

CO

N. R.

Complexation reduces the e- density on C6H6.

Reactivity towards Nu-:

increase

Reactivity towards E+:

decrease

Change the electron density distribution on L

:N

N:

:C

=0

unreactive

O:

=0

Upon complexation
M

-donation
M

N:

:N

N:

O:

:C

(e- to mainly C atom)

O:

- backdonation
M

overall

-N

N
-

N
-

Nu

C
M

E+

(e- to on both atom)

Nu-

O
-

E+

7. Differences between metals

1) Electronegativity differences:
Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

1.3

1.5

1.6

1.6

1.6

1.8

1.9

1.9

1.9

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

1.2

1.3

1.6

2.1

1.9

2.2

2.3

2.2

1.9

La

Hf

Ta

Re

Os

Ir

Pt

Au

1.1

1.3

1.5

2.3

1.9

2.2

2.2

2.3

2.5

Moving from left to right, the electronegativity of the elements increases

substantially.

2). Trend in the stability of high oxidation

states.
Early transition metals are electropositive, so they readily lose all their
electrons to give d0 centers (e.g. Zr(IV), Ta(V)). Low-valent early transition
metals, such as Ti(II) and Ta(III), are easily oxidized.
Late transition metals are more electronegative, thus they prefer lower
oxidation states (i.e., Rh(I) compared to Rh(III)).
Stability of high oxidation states

From left to right

From top to bottom
decrease
e.g. Ti(II) unstable

increase
Fe(II)

stable
Ti(IV) stable
exist

Fe(VIII) not

2). Trend in the relative energy of d orbitals and backdonation.

Question 1: Which of the following species has d electrons of highest
energy?
(1) (a) Ti(0)
(b) Ti(II)
(c) Ti(III)
(2)

(a)

(3)

Fe
Ru
Os

Ti2+

(b) Fe2+

(c) Ni2+

(d) Zn2+

Question 2. How would you explain the following trend in the IR dada of
(C-O) (in cm-1)?
a). V(CO)6
Fe(CO)5
CO
[Ag(CO)]+
1976
2023
2057
2204

b)

Cr(CO)6
W(CO)6

2000
1998

Effects of changing net ionic charge, ligands, and metal on the basicity of a metal
carbonyl, as measured by (CO) values (cm-1) of the highest frequency band in the IR
spectrum
Changing Metal
V(CO)6

Cr(CO)6

Mn2(CO)10

Fe(CO)5

Co2(CO)8

Ni(CO)4

1976

2000

2000

2023

2044

2057

Changing Net Ionic Charge in an Isoelectronic Series

[Ti(CO)6 ]2-

[V(CO)6 ]-

Cr(CO)6

[Mn(CO)6 ]+

[Fe(CO)6 ]2+

1747

1860

2000

2090

2204

Replacing -Acceptor CO groups by Non--Acceptor Amines

[Mn(CO)6 ]+

[(MeNH2)Mn(CO)5 ]+

[(en)Mn(CO)4 ]+

[(tren)Mn(CO)3 ]+

2090

2043

2000

1960

Question3.CompoundsoftheformulaMH4P3(M=Fe,RuandOs,P=PR3)
areknowntohavethefollowingstructure.
H

H
P
P

H H

P
H

Fe

P
P

Ru
H

H H

P
H
H

P
P

Os
H

H
P

P
P

Os
H H
whynot

Bonding picture of M(H2)

H
H

H (H )
2
H

1. e- from (H2) ---> (M)

H *(H2 )
H

2. e- from d(M) ---> (H2)

P
H?