Course Code: SC202(Chemistry)

Course instructor: Dr. Sangita talukdar

& DR. debarati mitra
Dept. of Science and Mathematics
IiitG, Guwahati
Lecture- Organometallic Chemistry
 Organometallic Chemistry

Definition: Organometallic chemistry is the chemistry of compounds containing metal-carbon bonds.

The first organometallic complex was prepared by W.C. Zeise in 1827, an ethene complex of platinum(II).

Zeise’s salt

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

 Classification of organometallic compounds

On the basis of nature of metal-carbon bond organometallic compounds are classified into
➢ Ionic bonded organometallic compounds:
The organometallic compounds of alkali, alkaline earth metals, lanthanides and actinides predominantly form ionic
compounds. These are generally colourless compounds extremely reactive, and insoluble in organic solvents.

Examples: Ph3C-Na+, Cs+Me-, Na+Cp-.

➢ Covalent bonded organometallic compounds:
1) σ- bonded organometallic compounds:
These are the compounds in which carbon atom of the organic ligand is bonded to the metal by a 2 electron, 2
centrered ( 2e-2c ) covalent bond.

Examples: Ni(CO)4, Fe(CO)5

2) π- bonded organometallic compounds:
These are the compounds of metals with alkenes, alkynes, benzene and other ring compounds. In these complexes,
the metal and ligand form a bond that involves the π-electrons of the ligand.
Examples:[(η5-C5H5)2Fe)], K[PtCl3(η2-C2H2)] (Zeise’s salt)
➢ Multicentre bonded organometallic compounds:
The compounds in which a loosely bonded electron deficient species exist with the coordination of metal like Li,
Be, Al…etc

Examples: Al2Me6
Electron counting and oxidation states
Two models are routinely used to count electrons, the so-called neutral-ligand method (sometimes called the
covalent method) and the donor-pair method (sometimes known as the ionic method).

(a) Neutral-ligand method

Count all valence electrons of the metal atom and all the electrons donated by the ligands.
If the complex is charged, add or subtract the appropriate number of electrons to the total.

Question 1: Do (a) [IrBr2(CH3)(CO)(PPh3)2] and (b) [Cr(η5-C5H5)(η6-C6H6)] obey the 18-electron rule?
Answer (a) We start with the Ir atom (Group 9) which has nine valence electrons, then add in the electrons from the
two Br atoms and the CH3 group (each is a one-electron donor) and finally add in the electrons from the CO and PPh3
(both are two-electron donors). Thus, the number of valence electrons on the metal atom is 9 + (3 x 1) + (3 x 2) = 18.

(b) In a similar fashion, the Cr atom (Group 6) has six valence electrons, the η5-C5H5 ligand donates five electrons,
and the η6-C6H6 ligand donates six, so the number of metal valence electrons is 6 + 5 + 6 = 17. This complex does not
obey the 18-electron rule and is not stable.
Table 1:Typical ligands and their electron counts

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

Table 2:Typical ligands and their electron counts
(b) Donor-pair method

1. Calculation of the oxidation number. The rules for calculating the oxidation number of an element in an
organometallic compound are the same as for conventional coordination compounds.
a.Neutral ligands, such as CO and phosphine, are considered to be two-electron donors and are formally
assigned an oxidation number of 0.

b. Ligands such as halides, H, and CH3 are formally considered to take an electron from the metal atom, and are
treated as Cl-, H-, and CH3-(and hence are assigned oxidation number -1); in this anionic state they are considered
to be two-electron donors. The cyclopentadienyl ligand, C5H5(Cp), is treated as C5H5 -(it is assigned an oxidation
number of -1); in this anionic state it is considered to be a six-electron donor.

2. The oxidation number of the metal atom is the total charge of the complex minus the charges of any ligands.
3. The number of electrons the metal provides is its group number minus its oxidation number.
The total electron count is the sum of the number of electrons on the metal atom and the number of electrons
provided by the ligands.
Question 2: Assign the oxidation number and count the valence electrons on the metal atom in (a)
[IrBr2(CH3)(CO)PPh3)2], (b) [Cr(η5-C5H5)(η6-C6H6)], and (c) [Mn(CO)5]-.

Answer (a) We treat the two Br groups and the CH3 as three singly negatively charged two-electron donors and the
CO and the two PPh3 ligands as three two-electron donors, providing 12 electrons in all. Because the complex is
neutral overall, the Group 9 Ir atom must have a charge of 3 (that is, have oxidation number 3) to balance the charge
of the three anionic ligands, and thus contributes 9 - 3 = 6 electrons.

This analysis gives a total of 18 electrons for the Ir(III) complex.

(b) We treat the η5-C5H5 ligand as C5H - and thus it donates six electrons, with the η6-C H ligand donating a further
5 6 6

six. To maintain neutrality, the Group 6 Cr atom must have a charge of +1 (and an oxidation number of +1) and
contributes 6 - 1 = 5 electrons. The total number of metal electrons is 12 + 5 = 17 for a Cr(I) complex.
Hapticity refers to the number of ligand atoms that are considered formally to be bonded to the metal atom. The
hapticity is denoted ηn, where n is the number of atoms (and η is eta).
For example, a CH3 group attached by a single M-C bond is monohapto, η1, and if the two C atoms of an ethene
ligand are both within bonding distance of the metal, the ligand is dihapto, η2. Thus, three cyclopentadienyl
complexes might be described as having η1 (4), η3 (5), or η5 (6) cyclopentadienyl groups.

η1-Cyclopentadienyl(4) η3-Cyclopentadienyl(5)

η5-Cyclopentadienyl(6)

7[Mo(η6-C6H6)(CO)3]
Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed
• Some ligands (eg., the hydride ligand, H-) can bond to more than one metal atom in the same complex, and are
then referred to as bridging ligands.

• The Greek letter μ(mu) is used to indicate how many atoms the ligand bridges.
• Thus a μ2-CO is a carbonyl group that bridges two metal atoms and a μ3-CO bridges three.

Nomenclature
Ligands are listed in alphabetical order followed by the name of the metal, all of which is written as one word.
The name of the metal should be followed by its oxidation number in parentheses.
For example, [Mo(η6-C6H6)(CO)3]
IUPAC name: benzene(tricarbonyl)molybdenum(0).

K[PtCl3(η2-CH2=CH2)] Potassiumtrichloro(ethene)platinate(II)
Question 3: : Give the formal names of (a) ferrocene [Fe(η5-C5H5)2 and (b) [RhMe(PMe3)4].
Answer (a) Ferrocene contains two cyclopentadienyl groups that are both bound to the metal atom through all five
carbon atoms, thus both groups are designated η5. The full name for ferrocene is thus
bis(η5-cyclopentadienyl)iron(II).
(b) The rhodium compound contains one formally anionic methyl group and four neutral trimethylphosphine
ligands, therefore the formal name is methyltetrakis-(trimethylphosphine) rhodium(I).

Question 4: What is the formal name of [Ir(Br)2(CH3)(CO)(PPh3)2]?

Metal-metal bonding and metal clusters

(a) Structure of clusters

A cluster includes all compounds with metal-metal bonds that form triangular or larger cyclic structures.

[Co4(CO)12]

(b) Electron counting in clusters

Mn2(CO)10
Each Mn atom is considered to have 17 electrons (seven from Mn and 10 from the five CO ligands). Mn-
Mn bond consists of two electrons shared between the two metal atoms, and hence raises the electron
count of each by 1, resulting in two 18-electron metal atoms.

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

• In Os3(CO)12, each Os(CO)4 fragment has 16 electrons before metal-metal bonding is taken into consideration
and three metal-metal bonds, so increasing the number of electrons around each metal to 18, but with a total of
only 48 and not 54 electrons

• The bonding electrons are referred to as the cluster valence electrons (CVEs), and a
cluster of x metal atoms with y metal-metal bonds needs 18x - 2y electrons.
• Octahedral M6 and larger clusters do not conform to this pattern, and the polyhedral
skeletal electron pair rules, known as Wade’s rules, have been refined by D.M.P. Mingos
and J. Lauher to apply to metal clusters. These Wade-Mingos-Lauher rules are
summarized in Table 3
Table 3: Correlation of cluster valence electron (CVE) count and structure

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed
(c) Synthesis of clusters
Three methods are commonly used to prepare metal clusters:
a. thermal expulsion of CO from a metal carbonyl,
One example is the synthesis of [Co4(CO)12] by heating [Co2(CO)8]:

2[Co2(CO)8] → [Co4(CO)12] + 4CO

In this case, a decrease in valence electrons around the metal resulting from loss of CO is compensated by the
formation of M-M bonds.

b. the condensation of a carbonyl anion and a neutral organometallic complex,

A widely used and more controllable reaction is based on the condensation of a carbonyl anion and a neutral
organometallic complex:

[Ni5(CO)12]2- + [Ni(CO)4] → [Ni6(CO)12]2- +4CO

The Ni5 complex has a CVE of 76 whereas the Ni6 complex has a count of 86. This type of reactions are called
redox condensation and are useful for the preparation of anionic metal carbonyl clusters.
c. the condensation of an organometallic complex with an unsaturated organometallic compound.
A third method, pioneered by F.G.A. Stone, is based on the condensation of an organometallic complex
containing displaceable ligands with an unsaturated organometallic compound. The unsaturated complex may
be a metal alkylidene, LnMCR2, a metal alkylidyne, LnMCR, or a compound with multiple metal-metal bonds:
Boron clusters
• B forms several series of neutral and anionic polymeric cage-like boron-hydrogen compounds called
borohydrides.

• Borohydrides are formed with up to 12 B atoms and fall into three classes called closo, nido, and arachno.
• The borohydrides with the formula [BnHn]2- have a closo structure, a name derived from the Greek for
‘cage’. This series of anions is known for n = 5 to 12, and examples include the trigonal-bipyramidal
[B5H5]2- ion (8), the octahedral [B6H6]2- ion (9), and the icosahedral [B12H12]2- ion(10).

8[B5H5]2- 9[B6H6]2- 10[B12H12]2-

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

• When boron clusters have the formula BnHn+4 they adopt the nido structure, a name derived from the Latin
for ‘nest’. An example is B5H9 (11).
• Clusters of formula BnHn+6 have an arachno structure, from the Greek for ‘spider’ (as they resemble untidy
spiders’ webs). One example is pentaborane (B5H11, 12).

(11)B5H9 (12)B5H11

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

 Table 4: Classification and electron count of boron hydrides

Question 6: Count the number of skeletal electrons in B4H10

Ans: We consider the number of BH units and the number of H atoms.
There are four BH units, which contribute 4 x 2 = 8 electrons, and the six additional H atoms, which contribute a further
six electrons, giving 14 in all.
The resulting seven pairs are distributed as shown in fig:
two are used for the additional terminal B-H bonds,
four are used for the four BHB bridges, and
one is used for the central B-B bond.

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

Question 6: Infer the structure of [B6H6]2- from its formula and from its electron count.
Answer We should note that the formula [B6H6]2- belongs to a class of borohydrides having the formula[BnHn]2-,
which is characteristic of a closo species.
Alternatively, we can count the number of skeletal electron pairs and from that deduce the structural type.
Assuming one B-H bond per B atom, there are six BH units to take into account and therefore 12 skeletal electrons
plus two from the overall charge of -2: 6 x 2 + 2 = 14, or seven electron pairs which is n + 1 with n = 6. This
number is characteristic of closo clusters. The closed polyhedron must contain triangular faces and six vertices;
therefore an octahedral structure is indicated.

Question 7: How many framework electron pairs are present in B4H10 and to what structural category does it
belong? Sketch its structure.
Organometallic compounds of the Group 1 elements

• Group 1 elements form a number of organometallic compounds that are unstable in the presence of water
and are pyrophoric in air.
• Sodium and potassium alkyls are produced by a transmetallation reaction, which involves breaking a
metal-carbon bond and forming a metal-carbon bond to a different metal. For example, methylsodium is
produced in the reaction between sodium metal and dimethylmercury in a hydrocarbon solvent:

• Organolithiums are the most important Group 1 organometallic compounds. They are liquids or low melting
solids, are the most thermally stable of the entire group, and are soluble in organic and nonpolar solvents
such as THF.
• They can be synthesized from an alkyl halide and lithium metal or by reacting the organic species with
butyllithium, Li(C4H9), commonly abbreviated to BuLi.

• Organolithium compounds are very important in organic synthesis, the most important reactions being those in
which they act as nucleophiles and attack, for example, a carbonyl group:
 Organometallic compounds of the Group 2 elements
Methylberyllium, Be(CH3)2 (13) , is predominantly a monomer in the vapour phase and in solid it forms polymeric
chains in which the bridging CH3 groups form 3c,2e bridging bonds. Bulkier alkyl groups lead to a lower degree of
polymerization; ethylberyllium (14) is a dimer and t-butylberyllium (15) is a monomer.

13(BeMe2)n, Me = CH3

14(BeEt2)2 15BetBu2, tBu = (CH3)3C

An interesting organoberyllium compound is beryllocene,

16(C5H5)2Be, in which the Be atom is positioned directly above
the centre of one cyclopentadienyl ring and below a single C atom
on the other ring.

16BeCp2, Cp = C5H5
Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed
Alkyl- and arylmagnesium halides are very well known as Grignard reagents and are widely used in synthetic
organic chemistry where they behave as a source of R–. The reaction to produce the Grignard reagents is carried
out in ether or tetrahydrofuran:

Mg(s) + RBr(sol)→RMgBr(sol)

Grignard reagents are widely used in the synthesis of organometallic compounds of other metals, as in the formation
of alkylberyllium compounds. They are also widely used in organic synthesis. One reaction is organomagnesiation,
which involves addition of the Grignard reagent to an unsaturated bond:

R1MgX (sol) + R2R3C=CR4R5(sol) → R1R2R3C=CR4R5MgX (sol)

Organometallic compounds of the Group 13 elements
The most important organometallic compounds of the Group 13 elements are those of B andAl.
(a) Organoboron compounds
• Organoboranes of the type BR3 can be prepared by hydroboration of an alkene with diborane.

• Like other B compounds, the organoboron species are electron deficient and consequently act as Lewis acids
and form adducts easily.
(b) Organoaluminium compounds
• Alkylaluminium compounds can be prepared on a laboratory scale by transmetallation of a mercury
compound:

17Al2(CH3)6
• In the dimeric halides, the bridging Al-Cl-Al bonds are 2c,2e bonds, that is each Al-Cl bond involves an
electron pair. In the alkylaluminium dimers the Al-C-Al bonds are 3c,2e bonds, with one bonding pair shared
across the Al-C-Al unit.
• Triethylaluminium and higher alkyl compounds are prepared from the metal, an appropriate alkene, and
hydrogen gas at elevated temperatures and pressures.

Triethylaluminium, often written as the monomer Al(C2H5)3, is used in the ZieglerNatta polymerization catalyst.

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

 Organometallic compounds of Group 14

Tin and lead form tetravalent organo compounds; organotin compounds are used as fungicides and
pesticides.

• The structures of R4Sn compounds are all similar, with a tetrahedral tin atom.
• The halide derivatives, R3SnX, often contain SnXSn bridges and form chain structures. The presence of
bulky R groups may affect the shape. For example, in (SnFMe3)n (18) , the SnFSn backbone is in a zig-
zag arrangement

18(SnFMe3)n, Me = CH3

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

Tetraethyl lead used to be made on a huge scale as an antiknock agent in petrol.
Alkyllead compounds, R4Pb, can be made in the laboratory by using a Grignard reagent or an organolithium
compound:

They are all monomeric molecules with tetrahedral geometry around the Pb atom. The halide derivatives may
contain bridging halide atoms to form chains. Monomers are favoured by more bulky organic substituents. For
example, Pb(CH3)3Cl exists as a chain structure with bridging Cl atoms whereas the mesityl derivative
Pb(Me3C6H2)3Cl is a monomer.

19(PbClMe3)n

Ref: Shriver & Atkins’ Inorganic Chemistry, 5th Ed

 Organometallic compounds of d-block elements

d-Block carbonyls
Homoleptic carbonyls
• A homoleptic complex is a complex with only one kind of ligand.
• The simple vanadium carbonyl V(CO)6 is an exception as it only has 17 valence electrons and is too sterically
crowded to dimerize; it is, however, readily reduced to the 18-electron V(CO)6 anion.
• The Group 6 hexacarbonyls are octahedral, pentacarbonyliron(0) is trigonal bipyramidal, tetracarbonylnickel(0) is
tetrahedral, and decacarbonyldimanganese(0) consists of two square-pyramidal Mn(CO)5 groups joined by a metal-
metal bond.
In 1890 Mond, Langer, and Quinke discovered that the direct combination of nickel and carbon monoxide produced
tetracarbonylnickel(0), Ni(CO)4, a reaction that is used in the Mond process for purifying nickel

50oC, 1 atm CO
Ni(s) + 4CO(g) Ni(CO)4(g)

Fe(CO)5, are synthesized at high pressures and temperatures

200oC, 200 atm

Fe(s) + 5CO(g) Fe(CO)5(l)
2Co(s) + 8CO(g) 150oC, 35 atm Co (CO) (s)
2 8
Synthesis and reactivity of cyclopentadienyl compounds

Cyclopentadiene itself is acidic enough that potassium hydroxide will deprotonate it in solution and, for
example, ferrocene can be prepared as follows:

2KOH + 2C5H6 + FeCl2 Fe(C5H5)2 + 2H2O + 2KCl

Because of their great stability, the 18-electron Group 8 compounds ferrocene maintain their ligand-metal bonds
under rather harsh conditions, and it is possible to carry out a variety of transformations on the cyclopentadienyl
ligands. For example, they undergo reactions similar to those of simple aromatic hydrocarbons, such as
FriedelCrafts acylation:

It also is possible to replace H on a C5H5 ring by Li:

Reactions
a. Ligand substitution

The substitution of ligands in organometallic complexes is very similar to the substitution of ligands in
coordination complexes, with the additional constraint that the valence electron count at the metal atom does not
increase above 18.

[Ir(CO)Cl(PPh3)2] + PEt3 → [Ir(CO)Cl(PPh3)2(PEt3)] → [Ir(CO)Cl(PPh3)(PEt3)] + PPh3

[V(CO)5(NO)] + PPh3 → [V(CO)4(NO)(PPh3)] + CO

[Re(η5-Cp)(CO)3] + PPh3 → [Re(η3-Cp)(CO)2(PPh3)] + CO
b. Oxidative addition and reductive elimination
Oxidative addition reactions result in two more ligands bound to the metal with an increase in the total electron
count at the metal of 2. Thus oxidative addition reactions normally require a coordinatively unsaturated metal
centre, and are particularly common for 16-electron square-planar metal complexes:

16e Pt(II) 18e Pt(IV)

The oxidative addition of hydrogen is a concerted reaction: dihydrogen coordinates to form a σ-bonded H2 ligand,
and then backbonding from the metal results in cleavage of the H-H bond and the formation of cis dihydrides:

Four-coordinate Five-coordinate Six-coordinate

16e Rh(I) 18e Rh(I) 18e Rh(III)
• In an SN2 oxidative addition reaction,a lone pair on the metal attacks the XY molecule displacing Y, which
subsequently bonds to the metal:

• There are two stereochemical consequences of this reaction. First, the two incoming ligands need not end up cis to
each other and, second, unlike the concerted reaction, any chirality at the X group is inverted. An SN2-type
oxidative addition is common for polar molecules such as alkyl halides.

• The opposite of oxidative addition, where two ligands couple and eliminate from a metal centre, is known as
reductive elimination:

18e Pt(IV) 16e Pt(II)

• Reductive elimination reactions require both eliminating fragments to be cis to each other.
c. σ-Bond metathesis
• A reaction sequence that is exchange of two species is known as σ-bond metathesis.
• σ-Bond metathesis reactions are common for early d-metal complexes where there are not enough electrons
on the metal atom for it to participate in oxidative addition.
• For instance, the 16-electron compound [ZrHMe(Cp)2] cannot react with H2 to give a trihydride as all its
electrons are involved in bonding to the existing ligands. A four-membered transition state is proposed in
such cases, and a concerted bond-making and bond-breaking step results in elimination of methane:
d. 1,1-Migratory insertion reactions

A 1,1-migratory insertion reaction is exemplified by reactions of the η1-CO ligand, where the following change
can take place:

• 1,1-Migratory insertion reactions result from the migration of a species such as a hydride or alkyl group to an
adjacent ligand such as carbonyl to give a metal complex with two fewer electrons on the metal atom..
• The overall reaction results in a decrease in the number of electrons on the metal atom by 2, with no change in
the oxidation state. It is therefore possible to induce 1,1-migratory insertion reactions by the addition of
another species that can act as a ligand:

[Mn(CH3)(CO)5] + PPh3 → [Mn(CH3CO)(CO)4PPh3]

e. 1,2-Insertions and β-hydride elimination

1,2-Insertion reactions are commonly observed with η2-ligands, such as alkenes and alkynes, and are exemplified by
the reaction:

1,2-Insertion reactions result in the formation of an η1 ligand with no change in oxidation state of the metal

Repetition of this process gives polyethene.

β-hydride elimination is the reverse of 1,2-insertion. The 1,2-insertion reaction, coupled with the β-hydride
elimination, can also provide a low-energy route to alkene isomerization:
f. α-, γ-, and δ-Hydride eliminations and cyclometallations
α -Hydride eliminations are occasionally found for complexes that have no β-hydrogens and the reaction gives
rise to a carbene that is often highly reactive:

γ-Hydride and δ-hydride eliminations are more commonly observed. Because the product contains a
metallocycle, a cyclic structure incorporating a metal atom, these reactions are normally described as
cyclometallation reactions:
 Identify the reaction type
a.

b.

a. oxidative addition reaction

In order to identify this reaction, we need to establish the valence electron counts and oxidation states of both the starting
material and the product. The four-coordinate squareplanar Rh starting material contains an η1-alkynyl ligand as well as three
neutral phosphine ligands; it is therefore a 16-electron Rh(I) species. The six-coordinate octahedral product contains two η1-
alkynyl ligands, a hydride ligand, and three neutral phosphine ligands; it is therefore an 18-electron Rh(III) species. The
increase in both coordination number and oxidation number by 2 identifies it as an oxidative addition.