10.1021/ja054885w.s002
Mark L. G. Borst
Mark L. G.
Borst
Rosa E. Bulo
Rosa E.
Bulo
Danièle J. Gibney
Danièle J.
Gibney
Yonathan Alem
Yonathan
Alem
Frans J. J. de Kanter
Frans
J. J. de Kanter
Andreas W. Ehlers
Andreas W.
Ehlers
Marius Schakel
Marius
Schakel
Martin Lutz
Martin
Lutz
Anthony L. Spek
Anthony L.
Spek
Koop Lammertsma
Koop
Lammertsma
3<i>H</i>-Benzophosphepine Complexes: Versatile Phosphinidene
Precursors
American Chemical Society
2005
benzophosphepine complexes
phosphinidene
hydrophosphination step proceeds
ML
diethynylbenzene
2005-12-07 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/3_i_H_i_Benzophosphepine_Complexes_Versatile_Phosphinidene_Precursors/3253207
The synthesis of a variety of benzophosphepine complexes [R = Ph, <i>t-</i>Bu, Me; ML<i><sub>n </sub></i>= W(CO)<sub>5</sub>,
Mo(CO)<sub>5</sub>, Cr(CO)<sub>5</sub>, Mn(CO)<sub>2</sub>Cp] 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.