ca01 only detailed ToC 1..24

1.1 Product Class 1:
Organometallic Complexes of Nickel
J. Montgomery
General Introduction
This contribution provides an overview of contemporary synthetic methods of broad applicability
that involve the preparation and use of nickel ð-complexes as starting materials
or reactive intermediates. Numerous excellent reviews on the chemistry of nickel
have appeared that are complementary to this contribution in subject and scope. An outstanding
review by Chetcuti describes the known ð-complexes of nickel, [1] and several
other structural classes of nickel complexes have been reviewed; [2–4] ó-bonded organonickel
compounds are reviewed in Houben–Weyl, Vol. 13/9b, pp 632–700. The historical development
and early applications of nickel chemistry have been reviewed by Wilke [5] and
Jolly, [6] industrial applications have been reviewed by Keim, [7] and several other reviews
on specific groups of synthetic transformations have appeared. [8–12,187] The organometallic
chemistry of nickel has a rich history dating back more than 100 years. [5] Despite its long
history, fundamentally new reactions are still being developed at a rapid pace. Furthermore,
existing reactions are being applied in new and creative ways to solve long-standing
challenges in organic synthesis. More and more of the synthetic organic community is
beginning to realize that nickel catalysis provides preparatively convenient reactions of
broad scope in a variety of contexts. In many cases, the reactivity exhibited by nickel may
not be achieved by any other transition element. At this time, organonickel chemistry
seems to be well poised to provide an increasing number of new reactions and interesting
mechanistic questions, as well as to gain an increasingly important role in the organic
chemist s repertoire of mainstream synthetic transformations.
The most commonly employed catalysts in nickel-catalyzed reactions are bis(acetylacetonato)nickel(II)
(1), which is commercially available, bis(ç 4 -cycloocta-1,5-diene)nickel(0)
(2) which is also commercially available or may be easily prepared (Scheme 1), [13]
and dichlorobis(triphenylphosphine)nickel(II) (3) which can also be easily prepared
(Scheme 2). [14]
SAFETY: Tetracarbonylnickel(0) should be handled with extreme caution due to its
volatility and high toxicity. All nickel compounds should be handled with care since
many are cancer suspect agents. [188]
Scheme 1 Synthesis of Bis(ç 4 -cycloocta-1,5-diene)nickel(0) [13]
Ni(acac)2
1
1. cod, THF, −78 oC 2. DIBAL-H, THF, −78 oC 72%
Ni(cod)2
2
Scheme 2 Synthesis of Dichlorobis(triphenylphosphine)nickel(II) [14]
NiCl 2•6H 2O
Ph 3P, AcOH, rt, 24 h
84%
NiCl2(PPh3) 2
3
31
for references see p 79