1,2-addition of diphosphine monoxide to a double bond of a titanocene carbene complex

Article abstract of DOI:10.1080/10426500213402

A titanocene carbene complex reacted with diphosphine monoxide to give R₂PCH₂PR₂.

Full text of DOI:10.1080/10426500213402

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
1,2-Addition of Diphosphine Monoxide to a Double
Bond of a Titanocene Carbene Complex
Jun-Ichi Ushio , Hiroaki Murakami , Tsutomu Mizuta & Katsuhiko Miyoshi
To cite this article: Jun-Ichi Ushio , Hiroaki Murakami , Tsutomu Mizuta & Katsuhiko Miyoshi
(2002) 1,2-Addition of Diphosphine Monoxide to a Double Bond of a Titanocene Carbene
Complex, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:8-9, 2167-2168, DOI:
10.1080/10426500213402
To link to this article: http://dx.doi.org/10.1080/10426500213402
Published online: 27 Oct 2010.
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Date: 08 June 2016, At: 16:13

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2167–2168
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290095016
1,2-ADDITION OF DIPHOSPHINE MONOXIDE TO A
DOUBLE BOND OF A TITANOCENE CARBENE
COMPLEX
Jun-Ichi Ushio, Hiroaki Murakami, Tsutomu Mizuta,
and Katsuhiko Miyoshi
Hiroshima University, Japan
(Received July 29, 2001; accepted December 25, 2001)
A titanocene carbene complex reacted with diphosphine monoxide to
give R2PCH2PR2.
A titanocene carbene complex exhibits various reactivities. For exam-
ple, it eliminates an oxygen atom from a carbonyl compound because of
strong affinity of titanium for oxygen,1 or it undergoes 1,2-addition of
E H bond (E Si, Ge, Sn).2 Since disphosphine monoxides 1a and 1b
in Scheme 1 have both P O bond and scissile P P bond, its reaction
with titanocene carbene is of interest. The results are shown below. 2a
and 2b are obtained when the reaction mixture is heated to 50 C in
benzene or toluene. It is proposed that the P P bond cleavage takes
place through a rearrangement shown in a bracket in the scheme. And
when 2a is heated up to 80 C, titanocene oxide is eliminated from 2a
to give a bisphosphine compound 3a.
SCHEME 1
Address correspondence to Katsuhiko Miyoshi, Department of Chemistry, Graduate
School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan. E-mail:
kmiyoshi@sci.hiroshima-u.ac.jp
2167

2168
J.-I. Ushio et al.
REFERENCES
[1] D. L. Hughes, J. F. Payack, D. Cai, T. R. Verhoeven, and P. J. Reider, Organometallics,
15, 663 (1996).
[2] Y. Hanzawa, N. Kuwase, and T. Taguchi, Tetrahedron Lett., 39, 583 (1998).