Reactions of phosphine oxides with bromophosphoranimines; synthesis and unusual rearrangements of O-donor stabilized phosphoranimine cations.
ABSTRACT Reaction of phosphine oxides R(3)P═O [R = Me (1a), Et (1c), (i)Pr (1d) and Ph (1e)], with the bromophosphoranimines BrPR'R''P═NSiMe(3) [R' = R'' = Me (2a); R' = Me, R'' = Ph (2b); R' = R'' = OCH(2)CF(3) (2c)] in the presence or absence of AgOTf (OTf = CF(3)SO(3)) resulted in a rearrangement reaction to give the salts [R(3)P═N═PR'R''O-SiMe(3)]X (X = Br or OTf) (X). Reaction of phosphine oxide 1a with the phosphoranimine BrPMe(2)═NSiPh(3) (5) with a sterically encumbered silyl group also resulted in the analogous rearranged product [Me(3)P═N═PMe(2)O-SiPh(3)]X (X) but at a significantly slower rate. In contrast, the direct reaction of the bulky tert-butyl substituted phosphine oxide, (t)Bu(3)P═O (1b) with 2a or 2c in the presence of AgOTf yielded the phosphine oxide-stabilized phosphoranimine cations [(t)Bu(3)P═O·PR'(2)═NSiMe(3)](+) ((+), R' = Me (d), OCH(2)CF(3) (e)). A mechanism is proposed for the unexpected formation of (+) in which the formation of the donor-stabilized adduct (+) occurs as the first step.