Synthesis and structure of a kinetically stabilized 1,3,6-triphosphafulvene

Full text of DOI:10.1080/10426500213341

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis and Structure of a Kinetically Stabilized
1,3,6-Triphosphafulvene
Hiroki Sugiyama , Shigekazu Ito & Masaaki Yoshifuji
To cite this article: Hiroki Sugiyama , Shigekazu Ito & Masaaki Yoshifuji (2002) Synthesis and
Structure of a Kinetically Stabilized 1,3,6-Triphosphafulvene, Phosphorus, Sulfur, and Silicon
and the Related Elements, 177:8-9, 2013-2014, DOI: 10.1080/10426500213341
To link to this article: http://dx.doi.org/10.1080/10426500213341
Published online: 27 Oct 2010.
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Date: 09 June 2016, At: 17:21

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2013–2014
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290094026
SYNTHESIS AND STRUCTURE OF A KINETICALLY
STABILIZED 1,3,6-TRIPHOSPHAFULVENE
Hiroki Sugiyama, Shigekazu Ito, and Masaaki Yoshifuji
Tohoku University, Japan
(Received July 29, 2001; accepted December 25, 2001)
Kinetically stabilized phosphanylidene carbenoid 1 is one of the pre-
cursors for novel low-coordinated phosphorus compounds. We report
the novel trimerization of phosphanylidene carbenoid 1 affording 1,3,6-
triphosphafulvene 3. Dibromophosphaethene 2 was allowed to react
with 2 molar equivalent of t-butyllithium at 78 C to generate the
phosphanylidene carbenoid 1, and the reaction mixture was warmed
to 25 C. After purification, 1,3,6-triphosphafulvene 3 was obtained
as a deep red solid. The NMR and MS spectrum of 3 supported the
1,3,6-triphosphafulvene structure. Furthermore, triphosphafulvene 3
was treated with an excess amount of W(CO)5(thf) to afford the pen-
tacarbonyltungsten(0) complex 3w as a deep red solid. Complex 3w
was recrystallized from toluene at 0 C to afford a suitable crystal for
x-ray analysis. The x-ray crystallography of 3w was confirmed the 1,3,6-
triphosphafulvene structure with the coordination of tungsten at the P3
position.1,
SCHEME 1
In ref. [1], the phosphorus chemical shifts at the P6 position for 3 and 3w should
read
= 399.0 and
= 397.1, respectively.
P
P
Address correspondence to Masaaki Yoshifuji, Department of Chemistry, Graduate
School of Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
E-mail: yoshifj@mail.cc.tohoku.ac.jp
2013

2014
H. Sugiyama et al.
REFERENCE
[1] S. Ito, H. Sugiyama, and M. Yoshifuji, Angew. Chem., Int. Ed., 39, 2781 (2000).