Synthesis and P–P cleavage reactions of [P(X)X′]2; X-ray structures of [Co{P(X)X′}(CO)3] and P4[P(X)X′]2 [X = N(SiMe3)2, X′ = NPri2]
Abstract
Treatment of P(X)(X′)Cl with KC8 gave the crystalline diphosphine [P(X)X′]2 (1) which dissociated reversibly into the phosphinyl radical ˙P(X)X′ (2), a plausible intermediate in the reaction of 1 with [Cr(CO)6], [Co(NO)(CO)3] or P4, yielding [Cr{P(X)X′}2(CO)3] (3), [Co{P(X)X′}(CO)3] (4), or 1,4-P4[P(X)X′]2 (5); the P(X)X′ substituent is pyramidal at P in 5 but planar in 4 [X = N(SiMe3)2, X′ = NPri2].