Organometallic Chemistry

An area which bridges organic and inorganic chemistry

A branch of coordination chemistry where the complex has one or more metal-carbon bonds
The leading journals of the field define an "organometallic" compound as one in which there is a
bonding interaction (ionic or covalent, localized or delocalized) between one or more carbon atoms of
an organic group or molecule and a main group, transition, lanthanide, or actinide metal atom (or
atoms).
Following longstanding tradition, organic derivatives of the metalloids such as boron, silicon,
germanium, arsenic, and tellurium also are included in this definition.
It is also understood that the element to which carbon is bound is more electropositive than carbon in
organometallic chemistry.
The metal-ligand interactions are mostly  acid type. M-C bond can be a  type or  type bond

NB: Traditional chemists do not agree for classifying metal cyanide complexes as organometallic
 Historical Background
 1760: As2O3 + 4CH3COOK [(CH3)2As]2O (Cadet’s Liquid)
[Cacodyl oxide]
 1827: K[PtCl3(η2-C2H4)].H2O Zeise’s salt
[1st Organometallic compound of transition metal]
 1849: 3C2H5I + 3Zn Et2Zn + C2H5ZnI + ZnI2 (Edward Frankland)
[Valuable synthetic reagent, spontaneously inflammable in air & are
difficult to handle]
 1890: Ni(CO)4 Mond Process
[Purification of Nickel]
 1900: RMgX Grignard Reagent
[More Versatile & have more application than organozinc reagent]
 1912: Nobel Prize to V Grignard & P Sabatier
[Grignard reagent & hydrogenation using metal powder]
 1917: 2Li + R2Hg 2RLi + Hg
2EtLi + Me2Hg 2MeLi + Et2Hg (Wilhelm Schlenk)
[1st alkyl-lithium derivatives by transalkylation of organomercury
compound]
 1932: R2CuLi Gilmann Reagent
 1938: Co2(CO)8 Oxo catalyst, Otto Roelen
[Hydroformylation catalyst]
 Historical Background Contd……
 1951: Ferrocene
 1955: (C6H6)2Cr
TiCl4/AlR3
 1955: CH2=CH2
 1962: trans-[Ir(CO)(Cl)(PPh3)2] Vaska’s Complex
 1963:
 1964: (OC)5W=C(Me)(OMe)
 1965: [Rh(PPh3)3Cl]
 1972: Heck Coupling
 1973:
 1979: Suzuki Coupling
Pauson & Kealy
[1st Sandwich Compound, structure was not discovered]
E. O. Fisher & W Hafner
CH3-(CH2-CH2-)n-CH3
[K. Zigler & G. Natta reports olefin polymerization]
[well known for the reversible addition of dioxygen, for the series of
other oxidative addition reactions that it undergoes with a large
number of substrates, including H2 at 25°C.]
Nobel prize to K. Ziegler & G. Natta
[for polymerization]
E. O. Fisher
[1st metal-carbene complex]
Wilkinson Catalyst (Wilkinson, Osborn, Coffey)
[Olefin Hydrogenation of alkene]
R F Heck & T Mizorki
[Pd catalyzed coupling of Vinylic Hydrogen atom with Aryl Halide]
Nobel Prize to G. Wilkinson & E. O. Fisher
[for Sandwich Complex]
Suzuki & Miyaura
[Pd catalyzed coupling of Aryl boronic acid with Aryl Halide]
 Historical Background Contd……
 1979: Brown & Wittig
[Hydroboronation]
 1990: Mo-catalyst Richard Schrock
[for Olefin metathesis]
 1995: Ru-catalyst Robert H. Grabbs
[for olefin metathesis]
 2005: Nobel Prize to Y. Chauvein, Richard Schrock, R. H. Grabbs
[Olefin metathesis]
 2005: Quintuple bond Philip Power
 2010: Nobel Prize to R. F. Heck, Ei-chi Neghishi, Akira Suzuki
[for metal mediated cross coupling reaction]
 The Ligands in Organometallic Chemistry
(a) L/Ln type: They are even ligands as they are bringing one or several electron pairs to the metal.
Designated as L or Ln , n being the number of electron pairs given to the metal.
The interaction of the ligands with metal are donor-acceptor type.

(b) X/XLn type: The ligands are bringing one or odd number of electrons to the metal, i.e., they are
radical type ligand and require one electron from the metal to make metal-ligand
bond.
The interaction of this type of ligand(s) with the metals resemble to the covalent bond
in organic chemistry as each partner brings one electron to form the bond electron
pair.
(c) Z type: These are Lewis acids, they bind to the metal in order to get their missing electron pair.
The most common ligands are the following:
 1-electron radical-type X ligands:
- H, F, Cl, Br, I
- OH, OR, SR, NR2, PR2, AsR2
- CH3, CR3 (alkyl), Ph, Ar (aryl), CH=CH2 (vinyl), COR (acyl), SiR3 (silyl), SnR3 (stannyl)
- NO (bent)
 2-electron X2 biradical type ligands:
- Carbene (triplet)
- =NR (amido), =PR (phosphinidenes), =O (oxo or oxene)
- -CH2(CH2)nCH2- (cycloalkyls), -O-O- (peroxide), O=C=O, S=C=S
 Ligands in Organometallic Chemistry Contd..
 2-electron L type ligands:
(non-bonding electron pair of an heteroatom)
- H2O, H2S, ROS, RSH, R2O, R2S
- NH3, NR3, PR3, P(OR)3, AsR3, SbR3
- N2, O2, CO, CS, RCN, RNC
(π-electron donor)
- alkene, alkyne, C=O bond of an aldehyde or ketone, O=O
(the donor of a σ bond electron pair)
X-Y Y=H, & X = H, C, Si, etc.
H-CR3 (intramolecular: C-H bond belonging to another ligand of the same metal by another bond)

 3-electron X3 type ligands:

- ≡CR (carbynes/alkylidynes), ≡N (nitride), ≡P (phosphide)
 3-electron XL type ligands:
- CH2=CH-CH2 (allyl), CHCHCH (cyclopropenyl)
- COOR (carboxylate), O2CNR2 (carbamato), S2CNR2 (dithiocarbamato), CH3COCHCOCH3 (acac)
- NO (linear)

 4-electron L2 type ligands:

- diammines (NH2CH2CH2NH2), diphosphines (R2P(CH2)nPR2), cis-butadiene, cyclobutadiene
 Ligands in Organometallic Chemistry Contd..
 4-electron LX2 type ligands:
- Oxo, imido type ligands (that are X2 ligands, can become LX2 ligands when the metal is electron-
deficient), nido-carborane (C2B9H112-) in its neutral form
 5-electron XL2 type ligands:
- C5H5 (cyclopentadiene, noted Cp), C6H7 (cyclohexadienyl)
 5-electron, X3L type ligands:
- The X3 nitrido and phosphido ligands can also become LX3 if the metal is electron deficient
 6-electron L3 type ligands:
π-donor: benzene, other aromatics and polyaromatics, borazine, cyclic triene
σ-donor: triamine, trisulphides, triphosphines

 6-electron L2X2 type ligands:

- Porphyrin, phthalocyanine

 7-electron XL3 type ligands: Cycloheptatrienyl

 8-electron L4 type ligands: Cyclooctatetraene (COT)
 Ambivalent Ligands in Organometallics
Ligands Type Number of Condition
electron
F, Cl, Br, I, OR, NR2, PR2, X 1
NO, allyl LX 3 According to metal need

L (singlet) 2 Electrophilic carbene

Carbenes X2 (triplet) 2 Nucleophilic carbene
Oxo, imido, phosphinidines X2 2
O, NR, PR LX2 4 According to metal need

Carbyne, ≡CH X3 3 Nucleophilic carbyne

LX 3 Electrophilic carbyne
Nitride, ≡N X3 3
LX3 5 According to metal need

Alkyne, RC≡CR L 2
L2 4 According to metal need
 Hapticity of the Ligands
Hapticity: Hapticity of a ligand may be explained as the number of ligand atoms simultaneously bound to
a metal centre.
with unsaturated ligand it is necessary to specify the no of carbon atoms which interact with the metal centre. The
prefix ηx before the ligand formula implies bonding to x carbon atoms. (NB: For ligands having all carbon atoms
bonded sometimes the superscript is omitted.)
Hapticity ligands Hapticity ligands

η1 Alkyl (-R), Aryl (-Ar), Perfluoroalkyl (RF), η5 Cyclopentadienyl derivatives,

(monohapto) Acyl (-COR), σ-allyl (-CH2-CH=CH2), σ- (pentahapto) Cycloheptadienyl derivatives
ethynyl (-C≡CR), CO, CS, CO2, CS2,
Carbenes (=CR2, =CR(OR), etc.),
Carbyne (-C≡C-R, -C≡C-Ar), Carbido (C)
η2 Alkene (R2C=CR2), Perfluoroalkene η6 Arenes (C6H6, substituted
(dihapto) (F2C=CF2), Alkyne (RC≡CR) (hexahapto) benzenes), Cycloheptatriene,
Cycloocta-1, 3, 5-triene
η3 π-allyl η7 Tropylium (Cycloheptatrienyl)
(trihapto) (heptahapto)
η4 cis-conjugated diene, cyclobutadiene η8 Cyclooctatetraene (COT)
(tetrahapto) derivatives (octahapto)
NB: Many ligand can bind with a metal in a more than one way. Allyl can be η1 (σ-allyl ) or η1 (π-allyl). Cyclooctatetraene can bind
to metal centre in different ways- η2 , η4 , η6 , η8.