UNIT 4

ORGANOMETALLIC CHEMISTRY
(METAL CARBONYLS)
ORGANOMETRALLIC CHEMISTRY

Definitions:

Organometallic compounds are compounds that possess one or more metal-carbon bond.
 The bond must be “ionic or covalent, localized or delocalized between one or more carbon
atoms of an organic group or molecule and a transition, lanthanide, actinide, or main group
metal atom.”

 Organometallic chemistry is often described as a bridge between organic and inorganic

chemistry.

 Organometallic compounds are very important in the chemical industry, as a number of them
are used as industrial catalysts and as a route to synthesizing drugs that would not have been
possible using purely organic synthetic routes.

Coordinative unsaturation is a term used to describe a complex that has one or more open
coordination sites where another ligand can be accommodated.

 Coordinative unsaturation is a very important concept in organotrasition metal chemistry.

Hapticity of a ligand is the number of atoms that are directly bonded to the metal centre.

 Hapticity is denoted with a Greek letter η (eta) and the number of bonds a ligand has with a
metal centre is indicated as a superscript, thus η1, η2, η3, ηn for hapticity 1, 2, 3, and n
respectively.

 Bridging ligands are normally preceded by μ, with a subscript to indicate the number of metal
centres it bridges, e.g. μ2–CO for a CO that bridges two metal centres.

Ambidentate ligands are polydentate ligands that can coordinate to the metal centre through one or
more atoms.

 For example CN– can coordinate via C or N; SCN– via S or N; NO2– via N or N. The term
can also be used to describe instances where a ligand can behave as monodentate or a
chelating ligand.

Bite angle is the ligand–metal–ligand angle formed when a polydentate ligand coordinates to a metal
centre.

A Chelate (Greek word for “claw” is a polydentate ligand that forms a ring that includes a metal.
Examples are EDTA, acac–, en.

Heterobimetallic describes a complex in which there are two different metal centres.

Homobimetallic complexes have two metal centres that are the same elements. These need not have
identical ligands or coordination number, but are usually found as symmetric dimers.

Homoleptic complexes are compounds in which all the ligands that bound to the metal centre are
identical.

A ligand is a molecule or ion that is bonded directly to a metal centre, usually by a covalent or
coordinate bond.

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Monodentate ligands have only one point of attachment to the metal centre and occupy one
coordination site only. Examples of monodentate ligands are NH3, CO, NMe3, H2O and PMe3.

Polydentate ligands have more than one point of attachment to the centre and occupy more than one
coordination site.

 By definitions above bidentate ligands and ambidentate ligands are special cases of
polydentate ligands.

The primary coordination sphere of a metal involves the set of ligands closest to the metal that are
directly bonded. Mobile cations and anions are said to be in the outer or secondary sphere.

HISTORICAL OVERVIEW OF ORGANOMETALLIC CHEMISTRY

Many examples of organometallic compounds involving alkyls, alkenes, alkynes, carbonyls and
aromatics are known.
Organometallic chemistry is a relatively recent area of chemistry (40-50 years), even though
organometallic compounds have been known since 1760; e.g. As2Me4O was made in 1760.
Some other historical landmarks are:

1827 Zeise’s salt: Na[PtCl3(C2H4)]

1849 Frankland: [(C2H5)2Zn]

1890 Mond: [Ni(CO)4] – the first binary metal carbonyl, and useful in purifying Ni

1931 Hieber: [Fe(CO)4H2] – the first hydride to be made.

1951 Ferrocene: [Fe(cp)2] – the first sandwich complex.

BONDING

 Bonding is essentially covalent and can be Metal–Carbon σ (as in metal carbonyls and
alkyls) or Metal–Carbon  bonds (as in metal alkenes, alkynes and arenes).

 Ionic compounds are often formed with electropositive metals, e.g. (C6H5)3C-–Na+ and (C5H5–
)2Ca2+. These ionic compounds are insoluble in hydrocarbon solvents and are very sensitive
to air and moisture.

ELECTRON COUNTING

The 18-electron rule

The 18-electron rule is like the octet rule to the organometallic chemists.

 It is useful in predicting the reactivity of organomettalic compounds.

 It is also often violated

 18-electron rule is also known as the effective atomic number rule (EAN rule).

 The rule is used to determine the number of valence electrons in a complex to determine
whether that complex is likely to be stable or not.
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  18 electrons arise from electrons from completely filled five d, three p, and one s orbitals.

 “A stable complex is obtained when the sum of metal d-electrons, the electron donated from
the ligands, and the overall charge of the complex equals 18.”

Counting electrons in organometallic complexes

Two distinct methods are used to count electrons: the neutral or covalent method and the effective
atomic number or ionic method.

 These are just two different methods of an accounting system that give the same final answer.
All you need to do is to understand one and keep to that to avoid confusion.

What are d-electrons

The configuration of transition metal as [Ar]4s23dn.

 This representation is only true for isolated metal atoms.

 When a metal ion is put into an electronic field (surrounded with ligands), the d-orbitals drop
in energy and fill first.

 The organometallic chemist therefore, considers the transition metal valence electrons to be
all the d-electrons.

 Thus a transition metal such as Ti in the zero oxidation state attains a d4, and not d2
configuration.

 Thus for zero-valent metals, the electron count simply corresponds to the column it occupies
in the periodic table. Fe, for example, in the 8th column is d8 and not d6; Re3+ is d4 (seventh
column for Re, and then add 3 position charges or subtract three negative ones).

 That is, d-occupancy = group number – oxidation state

Electronic contribution of ligands

Method 1: The ionic (charged) model

The basic premise of this method is that we remove all of the ligands from the metal and, if necessary,
add the proper number of electrons to each ligand to bring it to a closed valence shell state.

 For example, if we remove ammonia from a complex, NH3, has a completed octet and acts as
a neutral molecule. When it bonds to the metal centre if does so through its lone pair (in a
classic Lewis acid-base sense) and there is no need to change the oxidation state of the metal
to balance charge.

 Ammonia is called a neutral 2-electron donor.

 In contrast, if we remove a methyl group from the metal and complete its octet, then we
formally have CH3–.

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  If we bond this methyl anion to the metal, the lone pair forms one metal-carbon bond and the
methyl group acts as a 2-electron donor ligand.

 To keep charge neutrality we must oxidize the metal by one electron (i.e. assign a positive
charge to the metal). This, in turn, reduces the d-electron count of the metal centre by one.

Method 2: the covalent (neutral) model

The major premise of this method is that we remove all of the ligand from the metal, but rather than
take them to a closed shell state, we do whatever is necessary to make them neutral.
 Consider ammonia again: when we remove it from the metal, it is a neutral molecule with one
lone pair of electrons. Therefore, as with ionic, ammonia is a neutral 2-electron donor.
For methyl, we diverge from the ionic model. When we remove it from the metal and make the
fragment neutral we have a neutral radical.
 Both the metal and methyl radical must donate one electron each to form a metal-carbon
bond.

 The methyl group is, therefore, a one-electron donor, not a two-electron donor as it is under
the ionic formation.

 Notice that this method does not give us any immediate information about the oxidation state
of the metal, so we must go back and assign that later.

Some commonly encountered ligands donate the following numbers of valence electrons.

 1-electron donor: H• (in any bonding mode), and terminal Cl•, Br•, I•, R• (e.g. R = alkyl or Ph)
or RO•;
 2-electron donor: CO, PR3, P(OR)3, R2C=CR2 (η2-alkene), R2C: (carbine);
 3-electron donor: η3-C3H5• (allyl radical), RC (carbine), μ-Cl•, μ-Br•, -I•, μ-R2P•;
 4-electron donor: η4-diene, η4-C4R4 (cyclobutadienes);
 5-electron donor: η5-C5H5•, μ3-Cl•, μ3-Br•, μ3-I•, μ3-R2P•;
 6-electron donor: η6-C6H6 (and other η6-arenes, e.g. η6-C6H5Me);
 1- or 3-electron donor: NO

Counting electrons provided by bridging ligands, metal-metal bonds and net charges requires care.

 When X• (X = CI, Br, I) or R2P• the ligand uses the unpaired electron and a lone pair to bridge
two metal centres, i.e. one electron is donated to M, and two to the second metal, M´
 In a doubly bridged species such as (CO)2Rh(μ-Cl)2Rh(CO)2 the μ-Cl atoms are equivalent as
are the Rh atoms, and the two Cl bridges together contribute three electrons to each Rh.
 A bridging H• provides only one electron in total, shared between the metal atoms it bridges,
e.g. [HFe2(μ-CO)2(CO)6]–.
 M—M single bond provides each M atom with one extra electron; an M=M double bond
contributes two electrons to each metal.

Summary for 18-electron rule

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 1. Assume that the metal has an oxidation state of zero

2. Add or subtract electrons according to the overall charge on the complex

3. Add electrons from the ligands

4. Consider a M―M to provide one electron to each metal; an M=M bond to provide two
electrons to each metal.

5. Consider bridging two-electron ligands such as CO, CR2 to contribute one electron to each
metal.

Exceptions to the rule

1. Electron-rich complexes of d8 transition metals.

Metals such as Rh(1), Ir(II), Pd(II) have a strong preference for square planar 16-electron
configuration, e.g., [Ni(CN)4]2–, [PtCI3(η2-C2H4]–

2. High steric hindrance:

Ligands that are so bulky that not enough can be coordinated around a metal (there are few of
such metals at the left hand side of the transition metal series) to obtain 18-electron count.

CH3
H3C
CH3
(Me3Si)2HC
H3C CH3
Cr CH(SiMe3)2
Ti
(Me3Si)2HC
H3C CH3

CH3
H3C 9 VE
CH3

14 VE

3. Many organometallic compounds obey the 18-electron rule, but classical coordination
compounds often have widely differing electron counts. Why?
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  With 6 σ-donor ligands and the metal t2g and eg levels, three classes of complexes can
be seen:

 Class I:  is small: valence electron (VE) is less than or greater than 18. T2g is non-
bonding, eg is weakly antibonding. 12–22 VE can be accommodated.

e.g.: [TiF6]2– TiIV, d0 12 VE

[Mn(CN)6]3– MnIII, d4 16 VE
[Co(NH3)6]2+ CoII, d7 19 VE
[Zn(en)3]2+ Zn2+, d10 22 VE

 Class II: M is 2nd/3rd row transition metal and Δ is larger. VE is less than or equal to
18. T2g is nonbonding and occupied with 0-6 electrons, eg is antibonding and
unoccupied.

e.g.: WCl6 WVI, d0 12 VE

WCl62– WIV, d2 14 VE
PtF62– PtIV, d6 18 VE
PtCl42– PtII, d8 16 VE

 Class III: Δ large; VE = 18. These are organometallic complexes. T2g becomes
bonding and is fully occupied, eg is antibonding and empty. The 18-electron rule is
obeyed as far as steric constraints will allow.

e.g.: V(CO)6– V–, d6 18 VE

Fe(CO)5 Fe0, d8 18 VE
cpCo(CO)2 Co1, d8 18 VE
Ni(COD)2 Ni0, d8 18 VE

Examples:

Rationalize the following: Cr(CO)6, Ni(PF4)4, Fe(CO)4PPh3 and Mn2(CO)8

Answer:
Fe 8e- 2Mn 14e-
- -
Cr 6e Ni 10e 4CO 8e- 10CO 20e-
6CO 12e- 4PF3 8e- Ph3P 2e- Mn—Mn 2e-
18e- 18e- 18e- 36e- = 18e-/Mn

-BONDING LIGANDS

1. Common -bonding ligands are:

 Carbon monoxide
 Isocyanides, and
 Substituted phosphines, arsines, stibbines or sulfides,
 Nitric oxide (nitrogen(II) oxide), and
 Various molecules with delocalized -orbitals such as pyridines, 2,2-bipyridine, e.t.c.

2. Metals that could form complexes with the above ligands display low positive, zero, or
negative formal oxidation states.
3. Properties of complexes:
 These ligands then stabilize low oxidation states.
 This property is associated with the fact that in addition to lone pairs of electrons, the
ligands possess vacant -orbitals, which accept electrons density from filled metal orbitals
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 fo form a type of -bonding that supplements the -bonding arising from lone-pair
donation.
 The ability of ligands to accept electron density is then called -acidity (from Lewis
sense).

In this introductory lecture, we will limit ourselves to complexes of carbon monoxide.

METAL CARBONYL COMPLEXES

Ni(CO)4, the first metal carbonyl, was first discovered in 1888. Metal carbonyls belong to a very
important class of organometallic compounds. Almost all transition metals form compounds with
carbon monoxide as ligand.

Three important points about these compounds are:

 Carbon monoxide is not ordinarily considered a very strong Lewis base and yet it forms strong
bonds with the metals it complexes with.

 The metals are always in low oxidation state, usually 0, but sometimes +1 or -1.

 The 18-electron rule is obeyed by at least 99% of all the organometallic complexes.

Examples of stable carbonyl complexes of the first row transition metals are given in the Table
below.

Stable metal carbonyls

Mononuclear V(CO)6 Cr(CO)6 Fe(CO)5 Ni(CO)4

Dinuclear Mn2(C0)10 Fe2(CO)9 Co2(CO)8
Trinuclear Fe3(CO)12
Tetranuclear Co4(CO)12
Hexanuclear Co6(CO)16

 The only exception to the 18-electron among the mononuclear carbonyl complexes is
hexacarbonylvanadium(0), V(CO)6, which is paramagnetic and is a 17-electron molecule.

 V(CO)6 does not dimerise to give the 18-electron analogue like Mn2(CO)10 and Co2(CO)8
because each metal would attain a coordination number of 7, which may present too much
steric hindrance to allow stability.

 This may also be due to ligand repulsion that can overcome weak M—M bond or present a
kinetic barrier to dimerization.

 V(CO)6 is, however, less stable than other carbonyl complexes that obey the 18-electron rule.
It decomposes at 70 ℃ and readily forms [V(CO)6]– to form the 18-electron anion.

 The tendency to form more complex carbonyls increases from left to right in the first row
transition metal series.

 Second and third-row transition metals form parallel complexes to the ones given in the table
above; e.g. Mo(CO)6, Tc2(CO)10 and Re2(CO)10

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 Generally the carbonyls of the first row transition metals are more stable than their analogues
in the second and third row series. For example, Fe(CO)5 > Ru(CO)5 > Os(CO)5; Fe2(CO)9 >
Ru2(CO)9 > Os2(CO)9.

 Increasing strength of M—M interaction as one descends the transition metal series leads to
enhanced stability for Os3(CO)12 and Ru3(CO)12 relative to the mononuclear, M(CO)5.

Synthesis of metal carbonyls

(a) From the metal: By direct action of CO on finely divided metal. Only [Ni(CO)4] and
[Fe(CO)5] are so made.
o
Ni + 4 CO 25 C [Ni(CO)4]
1 bar

150oC
Fe + 5 CO [Fe(CO)5]
100 bar
 [Ni(CO)4] is a highly toxic colourless liquid; b.p. 34 oC. Purification of nickel by Monds
process is attained by decomposing [Ni(CO)4].
 [Fe(CO)5] is a yellow liquid; b.p. 103 oC. [Fe(CO)5] is very sensitive to light and heat and
decomposes in air.
 Photolysis of [Fe(CO)5] yields an orange yellow solid [Fe2(CO)9].

h
[Fe(CO))5] [Fe2(CO)9] (m.p. 100 oC)

(b) From metal salts: by reduction of metal salts in the presence of CO.

benzene, AlCl3
CrCl3 + Al [Cr(CO)6] + AlCl3
300 bar CO

AlEt3, PriO
Mn(OAc)2 + 10 CO [Mn2(CO)10]

 [Cr(CO)6] is colourless, diamagnetic, air-stable solid; m.p. is 154 oC. It has18 VE.
 [Mn2(CO)10] is a yellow crystalline, diamagnetic solid. It also obeys 18-electron rule.

300 bar CO
2 CoCO3 + 2 H2 + 8 CO [Co2(CO)8] + 2CO2 + 2H2O
130 oC

 [Co2(CO)8] is orange brown solid, diamagnetic; it obeys the 18-electron rule.

300 bar CO
2 CoCO3 + 2 H2 + 8 CO Co2(CO)8 + 2 CO2 + 2 H2O
130 oC orange-brown,
diamagnetic, 18 VE

STRUCTURES OF METAL CARBONYLS

Metals will bind enough CO ligands to obey the 18-electron rule.

Complexes can be monomeric or dimeric or trimeric – and feature metal-metal bonds to attain the 18-
electron configuration

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 Binary Transition-metal Carbonyl complexes

CO CO
CO OC
OC CO
Co CO
M
CO OC Co
OC
CO CO
OC CO
Solid state
M = V, Cr, Mo, W
OC
OC CO
Co
CO
OC CO OC
CO
Mn OC CO Co
OC Mn OC
CO CO
CO CO
OC CO Solution

Group 8

CO
OC Group 9: M = Co, Rh
M CO COCO
OC
OC
CO Ir
OC CO
M = Fe, Ru, Os Ir Ir
OC CO
CO CO Ir CO
OC OC
OC O
C CO OC OC CO
OC Fe CO
CO OC CO
Fe Fe Fe
OC CO CO
CO Fe OC
OC CO
OC C CO
O OC M
CO
O
CO OC C CO
OC CO
CO CO M M
M CO OC CO
OC M
OC CO
M M
CO OC CO
CO
OC
CO CO

M = Ru, Os

BONDING IN METAL CARBONYL

Two modes of bonding contribute to bonding of CO to metals:

a) Overlap of filled carbon p-orbital with a d-orbital of the metal to form a -type bond. Thus,
electron flows from carbon to metal. This increases the electron density on the metal atom. To
reduce the electron density the metal by pushing electron back to the ligand (back bonding).
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 M C O: M C O
+ e
-bond
Here the CO M(σ) ← CO(σ); M-C bond is strengthened

(b) Overlap of a filled d or hybrid dp—metal orbital with the empty p-orbital on CO, which can
act as a receptor of electron density. This constitutes a contribution from -bond.

M + :C O M :C O

e
-bond (M—L)

The * orbital accepts electron density from an occupied d-orbital. CO is therefore a strong -acid
This process is known as ‘back-bonding’. M—C Bond strengthened; C—O bond weakened
Both processes operate in opposite directions but are supportive i.e. Synergic bonding
The bonding mechanism is synergic, because back-bonding will tend to make the CO as a whole
negative (increasing its basicity); at the same time the electron drift to the metal in the -bond tends to
make the CO positive. In other words, the two effects assist each other.
The bond-order for M—CO bond is therefore greater than 1 but less than 2.

Physical evidence for bond-order/strength of M—CO bond

 Dipole moment of an M—C bond is very low (0.5 D)

 Bond length: Shorter M—C and longer C—O bonds as compared to single and triple bonds;
C—O bond is 1.128 Å, while in metal carbonyl complexes it is 1.15 Å.
 Vibrational spectroscopy (studying CO stretching frequencies): see below.

COORDINATION MODES OF CO
O
O O
C
C
O C M M
C M M M M
free terminal doubly triply
bridging bridging
 
CO 2143 2120-1850 1850-1750 1730-1620 cm-1

Doubly bridging is quite common.

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 CO CO CO
CO CO CO
OC Cr CO OC Mn Mn CO
OC OC
CO OC
CO CO
octahedral
octahedral
CO = 2000 cm -1
CO = 2044, 2013, 1983 cm-1

CO CO
OC
Fe CO Ni
OC CO
CO OC
CO
tetrahedral
trigonal bipyramid CO = 2057 cm-1
CO = 2034, 2013 cm-1

SPECTROSCOPIC CHARACTERIZATION OF METAL CARBONYLS

INFRARED SPECTROSCOPY

As mentioned above, the stretching frequency (CO) of the carbonyl bond can be very characteristic
and can be used to establish the mode of bonding of the gas. A number of factors determine the
stretching frequency of CO in any mode of bonding.

(i) Influence of charge

CO (cm-1)
d10 [Ni(CO)4] 2060
[Co(CO)4]– 1890
[F2(CO)4]2– 1790
d6 [Mn(CO)6]+ 2090
[Cr(CO)6] 2000
[V(CO)6]– 1860

Charge influences extent of back bonding

The higher the negative charge the greater the back bonding. The greater the back bonding the
stronger the M—C bond and the weaker the C—O bond.
The higher the positive charge the less the back bonding; the less the back boding the weaker the M—
C and the stronger the C—O bond.

(ii) Properties of other ligands

By replacing a CO group with a ligand which is a weaker -acceptor, then more electron deficient the
metal centre and the less efficient the back bonding (i.e. stronger C—O bond)

MASS SPECTROMETRY

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As neutral, volatile molecules, mass spectrometry is useful to observe parent molecular ions.
In addition, a sequential loss of carbonyl ligands can be seen and aids characterization.

O O

C C

M M
M
M
C
C

CO bridges often occur in pairs and can be in equilibrium with the non-bridging mode e.g.
O
O C
OC CO CO C CO
OC

CO Co Co Co Co Co
CO
C C CO
CO C O O C
O O

D3d C2V
(in solution)

5. REACTIVITY OF METAL CARBONYLS

(i) SUBSTITUTION REACTIONS

CO ligands can be substituted by other ligands, thermally or photochemically.

-CO L'
LnM - CO LnM LnM - L'
+CO
vacant
coordination
site

Second row complexes usually react faster than first- or third- row analogues.

(Some substitution reactions (typical) are shown in figure 7)

Photochemical substitution involves mild reaction conditions and allows synthesis of highly
substituted or more labile products.

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 hv L
Co2(CO)8 2 Co(CO)4. Co(CO)4. + Co(L) (CO)3.

18VE 17VE

Co2(CO)7L
18VE
product

(ii) REDUCTION (METAL CARBONYL ANIONS)

Reduction of metal carbonyls gives anionic complexes. They are highly reactive and there is rich
chemistry.
Fe(CO)5 + NaOH Na[H Fe(CO)4]-

NaH

Na2[Fe(CO)4]2-

THF
Co2(CO)8 + 2 Na 2 Na+[Co(CO)4]-

Carbonyl metallates are strong bases/nucleophiles and basicity increases within a group.

First < second < third

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