Spectroscopic Identification of Trifluorosilylphosphinidene and Isomeric Phosphasilene and Silicon Trifluorophosphine Complex.

The perfluorinated silylphosphinidene, F 3 SiP, in the triplet ground state is generated by the reaction of laser-ablated silicon atoms with PF 3 in solid neon and argon matrices. The reactions proceed with the initial formation of a silicon trifluorophosphine complex, F 3 PSi, in the triplet ground state, and a more stable inserted phosphasilene, FPSiF 2 , in the singlet ground state upon deposition. The trifluorosilylphosphinidene was formed through F-migration reactions of FPSiF 2 and F 3 PSi following a two-state mechanism under irradiation with visible light (λ = 470 nm) and full arc light (λ > 220 nm), respectively. High-level quantum-chemical methods support the identification of F 3 PSi, FPSiF 2 , and F 3 SiP by matrix-isolation IR spectroscopy.