%0 Journal Article
%A Borst, Mark L. G.
%A Bulo, Rosa E.
%A Gibney, Danièle J.
%A Alem, Yonathan
%A J. J. de Kanter, Frans
%A Ehlers, Andreas W.
%A Schakel, Marius
%A Lutz, Martin
%A Spek, Anthony L.
%A Lammertsma, Koop
%D 2005
%T 3H-Benzophosphepine Complexes: Versatile Phosphinidene
Precursors
%U https://acs.figshare.com/articles/journal_contribution/3_i_H_i_Benzophosphepine_Complexes_Versatile_Phosphinidene_Precursors/3253207
%R 10.1021/ja054885w.s002
%2 https://acs.figshare.com/ndownloader/files/5088568
%K benzophosphepine complexes
%K phosphinidene
%K hydrophosphination step proceeds
%K ML
%K diethynylbenzene
%X The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; MLn = W(CO)5,
Mo(CO)5, Cr(CO)5, Mn(CO)2Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is
discussed in detail. The first hydrophosphination step proceeds at ambient temperature without additional
promoters, and subsequent addition of base allows full conversion to benzophosphepines. Novel benzeno-1,4-diphosphinanes were isolated as side products. The benzophosphepine complexes themselves serve
as convenient phosphinidene precursors at elevated, substituent-dependent temperatures (>55 °C). Kinetic
and computational analyses support the proposal that the phosphepine−phosphanorcaradiene isomerization
is the rate-determining step. In the absence of substrate, addition of the transient phosphinidene to another
benzophosphepine molecule is observed, and addition to 1,2-diethynylbenzene furnishes a delicate bidentate
diphosphirene complex.
%I ACS Publications