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Metal CO Complexes
(18 Electrons Rule)

Metal Carbonyl
Carbonyl carbon monoxide , CO
Metal carbonyls are frequent starting materials
Metal carbonyls are known for most transition metals
Metal carbonyls are reactive labile CO is easily substituted
CO lost as gas is swept from system, pushes reaction forward
Metal carbonyls are easily studied by IR and provide information
on structure, symmetry, electron density changes at metal

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Carbonyl complexes
The carbonyl ligand forms a huge number of
complexes with metal ions, most commonly in low
oxidation states, where it binds to the metal through
its C-donor, as in the complexes below, where all the
metal ions are zero-valent:

[Ni(CO)4]
Td

[Fe(CO)5]
TBP (D3h)

[Cr(CO)6]
Oh

Metal-Carbon bonding in carbonyl

complexes
The carbonyl ligand is a -acid. This is an acid in the Lewis
sense, where it receives electrons from the metal ion, and it is
a acid because this involves -bonding. The -bonding
involves overlap of the * orbitals of the CO with d orbitals
from the t2g set of the metal, and so is d-p bonding. The
canonical structures involved in the -acid nature of CO are:

MCO
A

M=C=O
B

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Metal Carbonyls
Bonding in Metal carbonyls understood with MOT

-bonding: donation from M to LUMO on C

-bonding: donation
from HOMO on C

atomic
orbitals

CO

molecular
orbitals

atomic
orbitals

Carbonyl Complexes (CO)

Bonding
Review of CO Molecular Orbitals
HOMO resides mostly on C, -donation
LUMO resides mostly on C, -acceptance
Reinforce each other and provide strong bonding

Bonding of CO to a Metal

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Characteristics of CO complexes
Infrared Spectroscopy
Free CO stretch = 2143 cm-1
Cr(CO)6 CO stretch = 2000 cm-1 because -back donation from metal weakens
the CO bond by adding e- to antibonding * orbital

Negative charge on complex further weakens CO bond:

[V(CO)6]- = 1858 cm-1
[Mn(CO)6]+ = 2095 cm-1
d) Bridging CO further weakened by extra -back donation (e- count = 1/M)

X-Ray Crystallography
Free CO bond length = 112.8 pm
MCO carbonyl bond length = 115 pm

Metal-Carbon bonding in carbonyl

complexes
The carbonyl ligand is a -acid. This is an acid in
the Lewis sense, where it receives electrons from
the metal ion, and it is a acid because this
involves -bonding. The -bonding involves overlap
of the * orbitals of the CO with d orbitals from the
t2g set of the metal, and so is d-p bonding. The
canonical structures involved in the -acid nature of
CO are:

MCO
A

M=C=O
B

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Metal-Carbon bonding in carbonyl

complexes
What stabilizes CO complexes is MC bonding. The lower

the formal charge on the metal ion, the more willing it is to

donate electrons to the orbitals of the CO. Thus, metal ions
with higher formal charges, e.g. Fe(II) form CO complexes with
much greater difficulty than do zero-valent metal ions such as
Cr(O) and Ni(O), or negatively charged metal ions such as V(I). The overlap is envisaged as involving d-orbitals of the
metal and the *orbitals of the CO:

d-p*
overlap
d-orbital
of metal

* orbitals of CO
orbitals of CO

IR spectra and Metal-Carbon bonding in

carbonyl complexes
The CO stretching frequency of the coordinated CO is
very informative as to the nature of the bonding. Recall
that the stronger a bond gets, the higher its stretching
frequency. Thus, the more important the M=C=O (C=O
is a double bond) canonical structure, the lower the CO
stretching frequency as compared to the M-CO
structure (CO is a triple bond): (Note: CO for free CO
is 2041 cm-1)
[Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+
CO

1748

1858

increasing M=C double

bonding

1984

2094

2204 cm-1

decreasing M=C double

bonding

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IR spectra and bridging versus

terminal carbonyls
Bridging CO groups can be regarded as having a double
bond C=O group, as compared to a terminal CO, which is
more like a triple bond:
~ triple bond

M-CO
terminal carbonyl
(~ 1850-2125 cm-1)

the C=O group

in a bridging
M~ double bond carbonyl is more
like the C=O in
C=O
a ketone, which
typically has
M
C=O = 1750 cm-1

bridging carbonyl
(~1700-1860 cm-1)

One can thus use the CO stretching frequencies around

1700-2200 cm-1 to detect the presence of bridging CO
groups.

IR spectrum and bridging versus terminal

carbonyls in [Fe2(CO)9]
O
OC
OC

Fe
OC

CO
C
Fe
C
C O

CO

CO

terminal
carbonyls

bridging
carbonyls

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Organometallic Chemistry. Concepts.1

Predicting structure

18 electron Rule or Effective Atomic Number (EAN) Rule

a stable organometallic compound has 18 valence
electrons at the metal
Examples

The 18-electron Rule

Counting Electrons
The octet rule governs organic and simple ionic
compounds: s + 3p orbital
The 18-electron rule governs organometallics
(with many exceptions)
s + 3p + 3d orbitals
Donor ligands provide the electrons other than the delectrons

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Carbonyl complexes and the 18-electron rule

One might wonder why in the above complexes Ni(0)
has four CO groups attached to it, Fe(0) five CO,
and Cr(0) six CO. A very simple rule allows us to
predict the numbers of donor groups attached to
metal ions in organometallic complexes, called the
eighteen electron rule. The latter rule states that the
sum of the d-electrons possessed by the metal plus
those donated by the ligands (2 per CO) must total
eighteen:
[Ni(CO)4]
Ni(0)

4 x CO =

[Fe(CO)5]

[Cr(CO)6]

d10

Fe(0) =

d8

5 x CO

10

18 e

18e

Cr(0) =

d6

6 x CO = 12
18e

Formal oxidation states are all zero.

The Donor Pair method

of electron counting
(Method A)
Common organometallic

ligands are assigned an

electron count and charge
The charge on ligands
helps determine d-electron
count of metal
Add up all electrons from
Metal d orbitals and
ligands to find total ecount

(isonitrile or isocyanide)
(oxo, sulfido)

(nitrido)

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Carbonyl complexes and the 18-electron rule

To obey the 18-electron rule, many carbonyl
complexes are anions or cations, as in:
[V(CO)6]-

[Mn(CO)6]+

[Fe(CO)4]2-

V(0) = d5

Mn(0) = d7

Fe(0) = d8

6 CO = 12e

6 CO = 12e

4 CO = 8e

1-

= +1e

1+

= 18e
Formal oxidation
state = V(-I)

= -1e

2-

= 18e
Formal oxidation
state = Mn(I)

= 2e
= 18e

Formal oxidation
state = Fe(-II)

NOTE: In applying the 18-electron rule, metal ions are always

considered to be zero-valent, not the formal oxidantion state

Metal-Metal bonding in Carbonyl complexes

A species such as [Mn(CO)5] would have only 17 e.
The 18e rule can be obeyed by two such entities
forming a Mn-Mn bond, where each Mn contributes
one electron to the valence shell of the other Mn,
giving the metal-metal bonded species [(CO)5MnMn(CO)5]. To check on the 18e rule, we look at one
metal at a time:
Mn(0) = d7
Mn-Mn
bond
Mn

Mn

5 CO = 10
Mn-Mn = 1
18 e

[Mn2(CO)10]

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Bridging Carbonyls in carbonyl complexes

bridging
carbonyls

Co

Co

Co-Co
bond

[Co2(CO)8]

Carbonyls may form bridges

between two metals, where they
donate one electron to each
metal in working out the 18
electron rule. In [Co2(CO)8] at
left each Co has three terminal
COs, two bridging COs, and a
Co-Co bond:

Co(0)

d9

3 COs

2 bridge COs

Co-Co bond

1
18 e

Bridging Carbonyls in Fe2(CO)9

bridging
carbonyls

Fe-Fe
bond

[Fe2(CO)9]

Fe2(CO)9 has each Fe with

three terminal COs, three
bridging COs, and an FeFe
bond. The 18 electron rule
holds for each Fe atom as:
Fe(0)

d8

3 COs

3 bridge COs

Fe-Fe bond

1
18 e

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Charged ligands and the eighteen-electron rule

The formally charged ligands that are important in
organometallic chemistry are mainly soft ligands such as Cl-,
Br-, and I-, with CN- also occurring. Hydride (H-) is also very
important. These mono-anionic ligands all contribute one
electron for the 18-electron rule, as in the following examples:

[Mn(CO)5Cl]

[H2Fe(CO)4]

Mn(0)

d7

Fe(0)

5 COs

10

1 Cl

d8

Co(0)

4 COs =

4 COs = 8

2H

1H

18 e

[HCo(CO)4]

18 e

= d9

= 1
18 e

Examples of Electron Counting

Cr(CO)6
Total charge on ligands = 0, so charge on Cr = 0, so Cr = d6
6 CO ligands x 2 electrons each = 12 electrons
Total of 18 electrons

(5-C5H5)Fe(CO)2Cl
Total charge on ligands = 2-, so Fe2+ = d6
(5-C5H5- = 6) + (2CO x 2 = 4) + (Cl- = 2) = 12 electrons
Total of 18 electrons

Charged complex: [Mn(CO)6]+

Total ligand charge = 0, so Mn+ = d6
12 electrons from 6 CO ligands gives a total of 18 electrons

MM Bond: (CO)5MnMn(CO)5
Each bond between metals counts 1 electron per metal: MnMn = 1 e Total ligand charge = 0, so Mn0 = d7
5 CO ligands per metal = 10 electrons for a total of 18 electrons per Mn

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Justification for
and exceptions to
the 18-electron
Rule
MO Theory
predicts that 18
electrons fill
bonding orbitals
This number is
more stable than
more (filling
antibonding
orbitals) or less

When is the 18-electron rule most valid?

a) With octahedral complexes of large o.
b) Ligands are good -donors and good -acceptors (CO)

Exceptions to the 18-electron rule are common

Weak field ligands with small o make filling eg* possible ( > 18e-)
-donor ligands can make t2g antibonding ( < 18 e-)

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