Natural Organometallic Complex

Cyanocobalamin Methylcobalamin

Vit B12 - Cyanocobalamin - animals and humans can convert cyanocobalamin to

active (cofactor) forms of the vitamin, such as methylcobalamin.
 Recommended Text Books:

Organometallics, 3rd Edition by Christoph Elschenbroich. Wiley-

VCH, Weinheim. ISBN: 978-3-527-29390-2

Chemistry of the Elements, 2nd Edition by N.N Greenwood and

A. Earnshaw. Pergamon Press, 2nd Edition. ISBN: 0-7506-
3365-4

Inorganic Chemistry: Principles of Structure and Reactivity, by

James E. Huheey, Ellen A. Keiter, Richard L. Keiter. Prentice
Hall, 4 Edition. ISBN: 978-0060429959

Shriver and Atkins Inorganic Chemistry, 4th edition

Organometallic Chemistry: New Age International,

R.C. Mehrotra
 What is Organo-metallic?
Organic chemistry & Inorganic chemistry
• Strictly speaking, the chemistry of compounds containing at least one
metal-carbon bond.
• Metal hydrides are often included, H being considered as the "smallest organic
group" (as in propyl, ethyl, methyl, hydride).
• Metal-carbon bonds are often formed temporarily or potentially, so in
practice many compounds are included that do not actually contain metal-
carbon bonds. Where it is useful or Why it is important?

•Organometallic chemistry is the basis of homogeneous catalysis,

which is the method of choice for clean and efficient synthesis of fine
chemicals, pharmaceuticals and many larger-scale chemicals.
•Many plastics (polythene, polypropene, butadiene rubber, ...) and
detergents are made via organometallic catalysis.
•Organometallic chemistry is also the basis for understanding important
steps in heterogeneous catalysis reactions such as olefin
hydrogenation and CO oxidation.
•Organometallic compounds are used on a large scale as precursors for
generation of semiconductors (AlN, GaAs, etc).
•Silicone rubbers are one of the few classes of organometallic
compounds used as "final products".
History: First Organometallic Compound

Charles Louis Cadet

de Gassicourt

J. Chem. Educ., 1966, 43 (11), p 594

William Christopher Zeise

Danish organic chemist
Organometallics 2001, 20, 2-6
History: Organometallic Compounds
History: first organometallic
compounds
 1760 Louis Claude Cadet de Gassicourt (Paris) investigates inks
based on cobalt salts and isolates cacodyl from cobalt minerals
containing arsenic (CoAs2 and CoAsS2) :

As2O3 + 4 CH3COOK  [AsMe2]2 first organometallic compound

See editorial: Organometallics 2001, 20, 1488 -1498

 1827 Zeise’s salt is the first platinum - olefin complex

H H
EtOH Cl
KCl + PtCl2 Cl Pt K
- H2O
Cl
H H
See editorial: Organometallics 2001, 20, 2-6

7
History: 1900 – 1950
 1863 Charles Friedel and James Crafts prepare organochlorosilanes
 1890 Ludwig Mond discovers Ni(CO)4
 1893 Alfred Werner develops the modern ideas of coordination chemistry
 1899 introduction of Grignard reagents R
Mg R'-CO-R"
R X R MgX
Et2O OMgX
R'
R"
 1912 Nobel prize Victor Grignard and Paul Sabatier

1919, Hein: CrCl3 + PhMgBr [Cr(-Ph)n]0,+1 n = 2, 3, 4 Viktor-grignard

later:  complex 1912
 1917 Schlenk prepares Li alkyls via transalkylation from R2Hg
 1930 Ziegler and Gilman simplify organolithium preparation, using ether
cleavage and alkyl halide metallation, respectively
H
OC CO
Me Me Fe
Pt Fe
CO OC CO
Me I OC
CO H
first -alkyl complex
Pope, 1909 first dienecomplex first hydridecomplex
Reilhen, 1930 Hieber, 1931 8
History: 1950 – 1960
 1951 – 1952 Discovery of ferrocene, Fe(h5-C5H5)2
 Keally, Pauson, and Miller report the synthesis
 Wilkinson and Woodward report the correct structure

H
Fe Fe
H
Pauson, 1951
correct structure
Woodward and Wilkinson, 1952
 1973 Nobel prize Geoffrey Wilkinson and Ernst Otto Fischer on sandwich
compounds

 1955 Ziegler and Natta develop olefin polymerization at low pressure

using mixed metal catalysts (transition metal halide / AlR3)

Transition Metal
R2Al-R +
n
Catalyst

9
Ziegler/Natta polymerization
• Giulio Natta: Italian chemist, Nobel prize 1963
• Learned of Ziegler’s research, and applied findings to other a-olefins such as
propylene and styrene.
• Resulting polypropylene was made up of two fractions: amorphous (atactic) and
crystalline (tactic). Polypropylene is not produced in radical initiated reactions.

propylene polypropylene

Control of polymer tacticity:

X X X
Zr Zr Zr
X X X

racemic: C2 meso: Cs

1963 Nobel prize for Karl Ziegler and http://www.nobel.se/chemistry/laureates/1963/

Giulio Natta on Ziegler-Natta catalysts
History: 1960 – 1980:
catalysis
 1962: Vaska’s complex

O H
Ph3P O O2 Ph3P Cl H2 Ph3P H
IrIII IrI IrIII
OC PPh3 OC PPh3 OC PPh3
Cl Cl
Vaska's complex

 1964: Fischer reports the first metal carbene.

CO Br
OC CO OC CO
W W
OC CO OC CO
C C
Me OMe
Me
stabilized carbene complex carbyne complex
Fischer, 1964 Fischer, 1973

11
History: olefin metathesis
 1964: Banks reports the first example of olefin metathesis.

R1 R1 R2 R2 catalyst R1 R2
+ 2
R1 R1 R2 R2 R1 R2

 1971: Yves Chauvin proposes mechanism.

R R R
LnM LnM MLn

R' R' R' R' R' R'

 1974: Schrock synthesizes first metal alkylidene complex.

t
Bu
Cl
Cp
t
Me BuH2C
Ta Ta Ta C-tBu
CH2 Me2P
Cp
t
PMe2
t Bu
Bu Bu t first methylene complex
Schrock, 1975 first alkylidyne complex
first alkylidene complex
Schrock, 1976
Schrock, 1974
12
2005 Nobel prize in
chemistry
Schrock catalysts
ORf ORf
H H
RfO W Mo
t-Bu RfO
N CMe2Ph
N i
Pr
i i i
Pr Pr Pr F3C
O = ORf
F3C

Grubbs catalysts
PCy3
Cl
N N
Ru
Cl Ph Cl
PCy3 Ru
Cl
1st generation Ph
PCy3
2nd generation

13
 Georg Wittig
1951

E.O.Fischer 1974

G.Wilkinson

W.N.Lipscomb
1976
 Dorothy Crowfoot Hodgkin: 1964
Natural Organometallic Complex

Cyanocobalamin Methylcobalamin

Vit B12 - Cyanocobalamin - animals and humans can convert cyanocobalamin to

active (cofactor) forms of the vitamin, such as methylcobalamin.
Richard F. Heck: 2010

Akira Suzuki
 The Nobel Prizes in Organometallics

Karl Ziegler Giulio Natta William Lipscomb

1963 - Ethylene polymerization
1976- structure of boranes
Herbert C. BrownGeorg Wittig
1979 - olefins from phosphonium
ylides and carbonyl compounds &
Hydroboration

Kenichi Fukui
Dorothy Crowfoot Hodgkin Roald Hoffmann
1964 - Vitamin 1981 - Isolobal analogy
B12
2001- Enantioselective
catalysis
Geoffrey Wilkinson
Ernst Otto Fischer
1973 -sandwich
compounds 2005 - Olefin metathesis
 Nature of Bonding in
Organometallic Compounds!
 Nucleophiles Electropositive
Electrophiles Electron-rich
Electronegativ Electron-
e deficient
ucleophiles donate electrons (Lewis Bases)

ectrophiles accept electrons (Lewis Acid)

Electronegative: Ability of an atom to attract electrons (or

electron density) towards itself.

Electropositive: ability to donate electrons, and therefore form

positive ions. Metals, greater the metallic character, the greater
the electropositivity.
Electron-rich: Atoms that are willing to readily donate
electron pairs to other atoms are called electron rich. Ease of
ionization.
Electron-deficient (poor): Atoms that are NOT willing to
donate or share electron pairs to other atoms are called
electron deficient (poor).
 Organic chemistry:
 more or less covalent C-X
bonds
 rigid element environments
 fixed oxidation states (better:
valencies)

“Organometallic chemistry ? ”

Inorganic chemistry:
 primarily ionic M-X bonds, dative
M-L bonds
 variable and often fluxional
environments
 variable oxidation states
 “Organometallic chemistry” ??
Organometallics are more covalent

Knowledge of inorganic and coordination chemistry is useful to understand

geometries, electron counts and oxidation states of organometallic compounds

Organometallics are more covalent and often less symmetric than coordination
compounds, so orbital symmetry arguments are not as important

Organometallic chemistry is concerned with all metals, in combination with

all"organic" elements.

We concentrate on the M side of the M-C bond, and on how to tune its reactivity.
 Organic vs Organometallics

Organic Chemistry:
•C-C / C-H : nearly covalent
•Cδ+-Xδ-: polar (partly ionic)
•reactivity dominated by nucleophilic attack at C
•SN2 and SN1like reactivity

L
X
Organometallics: -L M +A
•C is the negative end of the M-C bond ("umpolung") X
L A
X X
M
•reactivity dominated by electrophilic attack at C M
X
L X L
•or nucleophilic attack at M X -L
X
+A
•associative and dissociative substitution at M A M
L L
Temperature without
drawing:
Side of the lit portion:
400 deg C (or 752 deg F)
Middle of the lit portion:
580 deg C (or 1112 deg
F)

Temperature during
drawing:
Middle of the lit portion:
700 deg C (or 1292 deg
F)
 Ligands
Classes of Ligands: Four generic classes of ligands:

L: a neutral electron pair donor (CO, PR3)

L-: an anionic electron pair donor (X-, H-)

L+: Cationic electron pair donor (Nitrosyl, NO+)

M-M: neutral 1 electron donor

Ligand Name Bonding Type Formal Electrons
Charge Donated
Molecular Hydrogen: H2 0 2

Hydride: H- M-H -1 2
Hydride: H- -1 2
Halide: X- M-X -1 2
Halide: X- -1 4
m bridging (2 to each M)
 How do I Figure
Out the Ligands??
 Nomenclature

Hapticity: A group of contiguous atoms of a ligand are

coordinated to a central atom.
η
- Indicated by the Greek character ' ‘

M
M
M M M
 Nomenclature
Denticity: If the coordinating atoms are not contiguous
(not connected to each other), the “Kappa” Κ-notation
is used

h1-dppe /
M PPh2 PPh2 k1-dppe

- bridging ligand
3
 18 Electron Rule

The Octet Rule: First row elements have 4 valence orbitals (1 s + 3 p)

so they can accommodate up to 8 valence electrons
 18 Electron Rule

The 18-Electron Rule :

•Transition metals have 9 valence orbitals (1 s + 3 p + 5 d).

•Upon bonding to a ligand set, there will be a total of 9 low lying
orbitals (bonding + non-bonding MO‘s).
•Therefore, we can expect that the low lying MOs can accommodate up
to 18 valence electrons
• Organometallic complexes
with 18 electrons are
predicted to be particularly
stable because they will have
a closed shell of electrons
(with electron configuration of
the next highest noble gas).

• Complexes with 18 electrons

are often referred to as being
coordinatively saturated
because there are no empty
low-lying orbitals to which
another incoming ligand can
coordinate.

•Complexes with counts lower

than 18e- are called
unsaturated and can
electronically bind additional
ligands.
 Exceptions to the 18e “Rule”

Early Transition Metals Middle Transition Metals Late Transition

Metals
16e- and sub-16e- 18e- configurations are 16e- and sub-16e-
configurations are common common configurations are common

Coordination geometries Coordination geometries of Coordination geometries of

higher than 6 relatively 6 are common 5 and lower are common: d8
common = square planar
Counting electrons: is the process of
determining the number of valence electrons about a
metal center in a given transition metal complex.

To determine the electron count for a metal complex:

1) Determine the oxidation state of the transition metal center(s)
and the metal centers resulting d-electron count. To do this one must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal
center (ionic ligand method)
c) know the number of electrons being donated to the metal
center from each ligand (ionic ligand method)
2) Add up the electron counts for the metal center and ligands
Counting electrons: There are two models for
counting electrons. Both gives the same answer.

Ionic Method & Neutral Method

Re(+1) d6
CH3 2 PR3 4e-
R3P CO 2 CO
4e-
Re CH3- 2e-
PR3 CH2=CH2 2e-
CO Total: 18e-

CNCH3 2+
H3CNC C NCH3
CNCH3
H3CNC Mo
Mo(+2) d4
H3CNC CNCH3 7 CNCH3 14e-
CNCH3 Total: 18e-
 Me
O O

R2 C C R2
P Cl P
Mo Mo
Rh P Cl P
R2 C C R2
PPh3 O O

Me Me
N H2 N
C Br
Pd Pd Ti
C Br
N H3 N
Me Me
 O O
O C C O
C C

OC
Fe ? Fe
CO

O
C C
O C Pd
O

O
C
Co ? Co
Fe
Ni
C
O