ORGANOMETALLIC CHEMISTRY OF

TRANSITION METALS

Session 1
Organometallic chemistry

 It is the study of chemical cpds containing bonds b/n carbon & a metal.
 combines aspects of inorganic chemistry & organic chemistry

benzene

Cr(0)

benzene
Definition of Organometallic compounds
 Compounds containing direct metal-carbon bonds of an organic molecule,
radical or ion.
 M-CH3 eg. CH3Li

 M-CO eg. Cr(CO)6

M-Arene eg. Cr(C6H6)2, Ferrocene

 C6H5Ti(OC3H7)3 (Alkoxide such as (C3H7O)4Ti is not considered to be

an organometallic cpd)
 Some cpds do not contain M-C bond, but they are usually included in the field of
organometallic chemistry. They include:

• Metal hydride complexes,

• Phosphine complexes

H PPh3 PPh3 PPh3

H Cl
Et3P Pt PEt3 Ph3P Rh PPh3 Ph3P Ru
Ph3P Ru H Cl
H2
Cl Cl PPh3
PPh3

• N2-complexes

2+ N
NH3
NH3 N
PPh2
H3N Ru N N Ph2P Mo PPh2
H3N Ph2P
NH3 N
N
The carbon cpds of B, As,Si,Tl & Ge are also considered as organometallic
cpds, excluding those of more EN atom.

Eg.

The bonding interaction must be ionic or covalent, localized or delocalized b/n one or

more C-atoms of an organic group or molecule .

The borderlines that distinguish organometallic chemistry from others
branches are sometimes unclear.
Eg. Ni(CO)4----OM cpds, but CO is inorganic cpd.

 Organometallic compounds of the transition metals have unusual structures, &

practical applications in organic synthesis & industrial catalysis.
 Organometallic vs classical complexes
M-X → if X=C..OM, X=hetroatom..classical complexes
Eg. M- carboxylates, M-ethylenediamine, M-water etc. are not OM cpds
Ox.state of metal → OM----lower than +2 ox.state ( +1,0, -1,-2)
eg. Ni(CO)4 , Fe(CO)5, HMn(CO)5
→ Classical complex…..+2 & higher ox.state.
Assignment of ox.state of the metal
 In Organometallic……Ambiguous/ very difficult.
eg. HMn(CO)5 ------ H+Mn-(CO)5 or H-Mn+(CO)5 or H0Mn0(CO)5

[Fe(C5H5)2] -----[Fe+2(C5H5-)2] or [Fe0(C5H5)02]

 In classical complex…….Very clear/easy
What makes OM cpds differ from organic cpds?
 Bond polarity;
 OM cpds have Mẟ+ - Cẟ- polarity while
Organic cpds have Mẟ- - Cẟ+ bond polarity ; M=O,N,F,Cl,Br,,,,
 Why organometallic chemistry ?
a). From practical point of view:
* OMC are useful for chemical synthesis, especially catalytic processes,
e.g. In production of fine chemicals
In production of chemicals in large-scale reactions could not be achieved
traditionally
Ar
N
OBn Mo
RO CMe2Ph
RO
+ H

OBn

CN Pd(PPh3)3 CN
+ Ph Ph + NEt3 + HNEt3I
I
Ph
Ph
* Organometallic chemistry is related to material sciences.
e.g. Organometallic Polymers
PBu3 PBu3
Pt C C C C Pt C C C C
n n
PBu3 PBu3

Small organometallic compounds:

Precursors to films for coating (MOCVD)

(η 3-C3H5)2Pd -----> Pd film

CH3CC-Au-CNMe -----> Au film

* Biological Science. Organometallic chemistry may help us to understand
some enzyme-catalyzed reactions.

H H H

C N
C

O
H2
Zn C
HN N N His-196
NH
O
CH2 H2
C C
His-69
O CH2

Glu-72

carboxipeptidase-A e.g. B12 catalyzed reactions.

b) From academic point of view:
* Organometallic compounds display many unexpected behaviors- discover
new chemistry- new structures e.g.

H H
H3N: M M M M
M M H SiR3

C C C C
M
M C M C

New reactions, reagents, catalysts, e.g.

Ziegler-Natta catalyst, Wilkinson catalyst  TiCl4 + Al(C2H5)3
Reppe reaction, Schwartz's reagent
Sharpless epoxidation, Tebbe's reagent
 Organo-transition Metal Chemistry History-Timeline
• 1760 - Cacodyl – tetramethyl diarsine, from Co-mineral with arsenic
(Main-group Organometallic cpd.)

• 1827 – “Zeiseʼs salt” –K[(C2H4)PtCl3]. H2O (1st organotransmetal cpd.!!)

Synthesis: PtCl4 + PtCl2 reflux in EtOH, then add KCl

Confirmed to have H2C=CH2 as a ligand in 1868
Structure not fully known until 1975
• 1863 - 1st metal-carbonyl, [PtCl2(CO)2]

• 1890 – L. Mond, reported the preparation of Ni(CO)4 (highly toxic) from

(impure) Ni & CO
(impure) Ni + xs CO –––> Ni(CO)4 (highly toxic)

• 1899 – 1912 Nobel Prize: Grignard reagents (RMgX )

(Main-group Organometallic cpd.)

• 1930 – Lithium cuprates, Gilman regent, formally R2Cu–Li+

General structure
In attempt to synthesize fulvalene

MgBr + FeCl3

Fulvalene

Produced an orange solid/powder (ferrocene)

Discovery of ferrocene began the era of modern organometallic chemistry.

i.e. Modern Organometallic Chemistry begins with this discovery
• 1951 – Ferrocene discovered in 1952 -- Sandwich structure
proposed

 Ferrocene was first prepared unintentionally: Pauson & Kealy, while setting
out with a goal to prepare fulvalene from cyclopentadieny-MgBr & FeCl3 ,
but, they unexpectedly obtained a light orange powder of "remarkable
stability.”, later accorded to aromatic character of Cp– groups.
 The sandwich cpd. led to new metallocenes chemistry (1973 Nobel prize,
Wilkinson & Fischer).
 The bonding nature in (Cp)2Fe allows the Cp rings to freely rotate, as
observed by NMR spectroscopy & Scanning Tunneling Microscopy  having
a Fluxional behavior(Note: Fe-C bond distances are 2.04 Å).
 1955-Cotton & Wilkinson Discovered fluxional behavior (or stereochemical
non-rigidity) of organometallics complex
 Fluxional behavior is defined as the capability of a molecule to undergo fast
and reversible intramolecular isomerization, to which the energy barrier is
lower than that allowing for the preparative isolation of the individual isomers
at room temperature.
 It is conventional to assign stereochemically non-rigid systems to those cpds
whose molecules rearrange rapidly enough to influence NMR line shapes at T’s
within the practical range (–100 °C to +200 °C ) of experimentation.
 An example of a fluxional
organometallic cpd. of Ru
 1961 – D. Hodgkin, X-ray structure – Coenzyme Vitamin B 12; it is the oldest
organometallic complex (because of its biological importance) Naturally
occurring Cobalimins contain Co—C bonds
 1963 - Ziegler/Natta (Nobel Prize) - alkene polymerization catalysts
 1964 – Fischer carbene; the 1st Metal - carbene complex

 1965 – Cyclobutadieneiron tricarbonyl, (C4H4)Fe(CO)3

 (C4H4) alone is non-aromatic (with 4 π-electrons);
 But with the Fe(CO)3, (C4H4 ) behaves as aromatic
gaining 2 π from Fe
 1965 – Wilkinson hydrogenation catalyst, Rh(PPh3)3Cl
 1971 – Monsanto Co. – Rh catalyzed acetic acid synthesis
 1973 – Commercial synthesis of L-Dopa (Parkinson's drug) asymmetric catalytic
hydrogenation;
 The 2001 Nobel Prize – awarded for their work in catalytic asymmetric synthesis to
W. S. Knowles (Monsanto Co.), R. Noyori,, (Nagoya, Japan), K. B. Sharpless (Scripps,
USA)

 1982, 1983 – oxidative addition of saturated hydrocarbon, including CH4

 1983 – Agostic interactions (structures)
AGOSTIC INTERACTIONS:

 Agostic – derived from the Greek word for "to hold on to oneself”
C-H bond on a ligand that undergoes an interaction with the metal
complex resembles the transition state of an oxidative addition or
reductive elimination reaction.
 Agostic C-H bond can be detected by IR, NMR and XRD techniques;
 In the cpd. above: the Mo–H bond distance = 2.1 Å, two IR bands
observed at 2704 & 2664 cm–1 and the agostic proton observed at δ = 3.8
ppm.
 The two hydrogens on the agostic methylene are rapidly switching b/n
terminal and agostic on the NMR time scale.
Nobel -Prize Winners related to the area:

Victor Grignard and Paul Sabatier (1912)

Grignard reagent ----convert Carbonyl to alcohol

K. Ziegler, G. Natta (1963)

Zieglar-Natta catalyst

E. O. Fisher, G. Wilkinson (1973)

Sandwich compounds

K. B. Sharpless, R. Noyori (2001)

Hydrogenation & oxidation

Yves Chauvin, Robert H. Grubbs, Richard R. Schrock (2005)

Metal-catalyzed alkene metathesis
 Common organometallic Ligands & nomenclature

Important ligands for organometallic complexes are:

C≡O The carbonyl ligand
PR3 The phosphines, where R is, for example –CH3 or

-C6H5 (trimethyl phosphine and triphenylphosphine).

ethylenes, butadiene, cyclooctadiene, cycopentadienyl anion:

butadiene cyclooctadiene (COT) cyclooctatetraene (COD) cyclopentadienyl

anion
M H M C M C
C M M

M CO M CNR M N2
H H
M CS M NO M PR3 M M
H X

M M M M
M
M

M C

M C
 Binding Modes
1. Bridging is possible with organometallic ligands
 The symbol, μ, indicates bridging; normally we have μ2 & rarely μ3 bridging

2) Different numbers of atoms of the organometallic ligand may be

involved in bond & is called the “Hapticity” of the ligand
End of Session 1