Flash vacuum thermolysis: First gas-phase generation of unhindered silylidenephosphanes and characterization by photoelectron spectroscopy

V. Lefèvre , J.L. Ripoll , Y. Dat , S. Joantéguy , V. Métail , Anna Chrostowska (1) , G. Pfister-Guillouzo

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

The flash vacuum thermolysis of cyclodisilaphosphanes, cyclotrisilaphosphanes, and a phosphasilacyclobutane, potential precursors of unhindered silylidenephosphanes (R2Si=PR′), has been investigated by NMR as well as by coupling with HRMS and, particularly, photoelectron spectroscopy. This last technique led us to characterize for the first time, in the gas phase, two very reactive species of this series, the P-tert-butyl- and P-phenyl-(dimethylsilylidene)phosphanes (Me2Si=P-t-Bu and Me2Si=PPh). The first ionization potentials at weaker energy are associated with the ejection of an electron from the πSi=P bond. The ionizations of the lone pair on phosphorus are observed at higher energy.

Domaines: Chimie inorganique; Chimie organique

V. Lefèvre, J.L. Ripoll, Y. Dat, S. Joantéguy, V. Métail, et al.. Flash vacuum thermolysis: First gas-phase generation of unhindered silylidenephosphanes and characterization by photoelectron spectroscopy. Organometallics, 1997, 16 (8), pp.1635--1640. ⟨hal-01566363⟩