MINIREVIEW
substituent R at the organophosphorus ligands. Thus, the
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cation derived from 49c (R Ph) exhibited the highest
[
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À1 À1
activity (128 kg polyethylene molPd
h
yielding a polymer
1
À1
with a molecular weight of 18700 gmol , which well com-
[
pares with the activity of Pd/diimine catalysts.[
39, 44]
Best
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[
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results were obtained at 708C and at a pressure of 9.81 Â
5
1
0 Pa. Catalyst activity remained unchanged at higher
[
6] For reviews see: a) M. Regitz, O. Scherer, Multiple Bonds and Low
Coordination in Phosphorus Chemistry, Thieme, Stuttgart, 1990;
b) K. B. Dillon, F. Mathey, J. F. Nixon, Phosphorus: The Carbon
Copy, Wiley, Chichester, 1998.
pressures, although the average molecular weight decreased
significantly. A remarkable feature of Yoshifuji×s catalyst is its
thermal stability, up to 1008C no tendency for decomposition
was noticed.[43]
Test reactions revealed, that the h -phosphabenzene iron
[7] K. Weissermel, H.-J. Arpe, Industrielle Organische Chemie, VCH,
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6
[
[
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complex 50 catalyzes the cyclotrimerization of dimethyl
acetylenedicarboxylate to give C (CO Me) and the co-cyclo-
6
2
6
trimerization of butyronitrile and alkynes to afford pyridine
derivatives. The efficiency of 50, however, is far below that of
classical CpCo catalysts.[ Similar observations were made
for the dimerization of 1,3-butadiene to give 1,5-cycloocta-
diene under the catalysis of complex 51.[
[
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46]
[
[
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From the results discussed here it is clear that heterocycles
with low coordination number phosphorus atoms such as
phosphabenzenes and mono- and diphosphaferrocenes are
valuable as efficient modifying ligands in homogeneous
catalysis. A number of papers underline their pronounced p-
acceptor capability, which makes phosphabenzenes and
phosphaferrocenes ideal as ligands for the soft metal centers
usually present in catalytically active complexes. Planar-chiral
structures at the ferrocene framework are prerequisites for
the well-tailored design used in enantioselective, asymmetric
syntheses.
[
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[
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The remarkable results, achieved by less than 10 research
groups and in less than 10 years of research activity in this
area of academic and commercial interest, are promising for
the future development and improvement of highly efficient
and stereoselective catalysts. Without exaggeration the chem-
istry of phosphorus ± carbon heterocycles may well be re-
Asymmetry 1997, 8, 2607; c) C. Ganter, C. Kaulen, U. Englert,
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2
garded as a gold mine for new sp -ligands which are able to
confer unusual properties upon metal centers and the
substrates there coordinated.
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The author is grateful to Prof. B. Breit, Prof. G. C. Fu, Prof.
F. Mathey, Prof. M. Yoshifuji, and Dr. P. LeFloch for valuable
discussions and unpublished results.
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Received: September 6, 2001 [M1530]
Angew. Chem. Int. Ed. 2002, 41, No. 4
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