Organometallic
Compunds
12/5/2018 D. JIM LIVINGSTON, [Link] in Chemistry,
[Link]’s College, Palai.
What is organometallic chemistry?
Compounds having at least one bond between carbon of
an organic functional group and metal are known as
organometallic compounds
In many compounds, both σ- and π-bonding exist
between the metal
(AlMe3)2
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
A brief history of organometallic chemistry
Organometallic Vitamin B12
Chemistry has
really been around
for millions of
years
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Naturally occurring Cobalimins contain Co—C
bonds
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Tetramethyldiarsine
1st organometalic compound - Louis Claude Cadet de Gassicourt
French chemist
organoarsenic compound – aka Cacodyl or dicacodyl
Greek kakodes (evil-smelling)
It is a poisonous oily liquid with an extremely unpleasant garlicky odor.
“when one is exposed to the smell of these compounds the tongue becomes
covered with a black coating even when no further evil effects are
noticeable". Bunsen's words
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Zeise's salt
William Christopher Zeise
potassium trichloro(ethene)platinate(II) -K[PtCl3(C2H4)]·H2O.
1st example of a transition metal alkene complex
yellow, coordination complex contains an η2-ethylene ligand with a square
planar geometry..
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Diethylzinc or DEZ
a highly pyrophoric and reactive organozinc compound
colourless liquid used in organic synthesis as a source of the ethyl carbanion
in addition reactions to carbonyl groups.
high reactivity toward air, it was used in small quantities as a hypergolic or "self
igniting" liquid rocket fuel.
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Nickel tetracarbonyl
This pale-yellow liquid an intermediate in the Mond process for the
purification of nickel and a reagent in organometallic chemistry.
Nickel carbonyl is one of the most toxic substances encountered in
industrial processes
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Grignard reagent,
Victor Grignard 1912 Nobel Prize
organic derivatives of magnesium (Mg)
RMgX
R is a hydrocarbon radical: CH3, C2H5, C6H5, etc.; and X is a halogen atom,
usually chlorine, bromine, or iodine.
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Applications
in the industrial production of Tamoxifen currently used for the treatment of
positive breast cancer in women
sold under the brand name Nolvadex
Tamoxifen is used to treat infertility in women with anovulatory
disorders
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Gilman Reagent
American chemist Henry Gilman – 1930
organocopper compounds
lithium dimethylcopper reagentsimilar to
Grignard reagents.
used for carbon-carbon bond formation in
organic synthesis
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Ferrocene
Ferrocene (metallocene) a type of organometallic chemical compound
consisting of two cyclopentadienyl rings bound on opposite
sides of a central metal atom.
Discovered in 1951.
known as sandwich compounds.
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
antiknock agents used in the fuel for petrol engines
they are safer than tetraethyllead, previously used
Ferroquine (7-chloro-N-(2-
((dimethylamino)methyl)ferrocenyl)quinolin-4-amine),
an antimalarial.
a precursor to iron nanoparticles, can be used as a
catalyst for the production of carbon nanotubes
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Ziegler–Natta catalyst
Karl Ziegler Giulio Natta
Titanium compounds in combination, organoaluminum compounds.
used to polymerize terminal alkenes (ethylene and alkenes with the vinyl double
bond)
1963 Nobel Prize
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Transition metal carbene
complex
organometallic compound featuring a divalent
organic ligand
Fischer -1964 (CO)5W=C(Ph)(OMe)
Classified into two types. Fischer carbenes,
Schrock carbenes
These are heterogeneous catalysts used for
alkene metathesis
1973 - the Nobel Prize in Chemistry
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Alkene Metathesis
Alkene metathesis or Olefin metathesis is an organic reaction
that entails the redistribution of fragments of alkenes (olefins) by
the scission and regeneration of carbon-carbon double bonds
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Robert Grubbs
Alkene Metathesis Richard Schrock
awarded the 2005 Nobel Prize in Chemistry.
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Palladium-catalyzed coupling
reactions
cross-coupling reactions that employ palladium complexes as catalysts.
active area of research and applications in homogeneous catalysis.
In 2010, the Nobel Prize in Chemistry was awarded to Richard F. Heck,
Ei-ichi Negishi, Akira Suzuki
Typical palladium catalysts used include the following compounds:
palladium acetate, Pd(OAc)2
tetrakis(triphenylphosphine)palladium(0), Pd(PPh3)4
bis(triphenylphosphine)palladium(II) dichloride, PdCl2(PPh3)2
[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichlorideard F.
Heck, Ei-ichi Negishi and Akira Suzuki
D. JIM LIVINGSTON, AP (Chem)
12/5/2018
Heck reaction (coupling reaction)
Coupling reaction - two hydrocarbon
fragments are joined together with the
aid of a metal catalyst.
Heck reaction - an unsaturated halide (or triflate) with an alkene in the
presence of a base and a palladium catalyst (or palladium nanomaterial-
based catalyst) to form a substituted alkene
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Suzuki coupling
Suzuki reaction is an organic reaction, classified as
a coupling reaction, where the coupling partners
are a boronic acid and an organohalide
catalyzed by a palladium(0) complex
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Sonogashira reaction
a cross-coupling reaction employs a palladium
catalyst as well as copper co-catalyst.
Formation of carbon–carbon bond between a
terminal alkyne and an aryl or vinyl halide
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
Stille reaction
The Stille reaction involves the coupling of an organotin
compound (organostannanes) with a variety of organic
electrophiles via palladium-catalyzed coupling reaction
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
12/5/2018 D. JIM LIVINGSTON, AP (Chem)
![Zeise's salt
William Christopher Zeise
potassium trichloro(ethene)platinate(II) -K[PtCl3(C2H4)]·H2O.
1st example of a tr](https://screenshots.scribd.com/Scribd/252_100_85/189/395039929/6.jpeg)
