Inorganic Chemistry p. 10292 - 10302 (2011)
Update date:2022-08-04
Topics:
Bendle, Martin
Huynh, Keith
Haddow, Mairi F.
Manners, Ian
Reaction of phosphine oxides R3P=O [R = Me (1a), Et (1c), iPr (1d) and Ph (1e)], with the bromophosphoranimines BrPR′R″P=NSiMe3 [R′ = R″ = Me (2a); R′ = Me, R″ = Ph (2b); R′ = R″ = OCH2CF3 (2c)] in the presence or absence of AgOTf (OTf = CF3SO3) resulted in a rearrangement reaction to give the salts [R3P=N= PR′R″O-SiMe3]X (X = Br or OTf) ([4]X). Reaction of phosphine oxide 1a with the phosphoranimine BrPMe2=NSiPh3 (5) with a sterically encumbered silyl group also resulted in the analogous rearranged product [Me3P=N=PMe2O-SiPh3]X ([8]X) but at a significantly slower rate. In contrast, the direct reaction of the bulky tert-butyl substituted phosphine oxide, tBu3P=O (1b) with 2a or 2c in the presence of AgOTf yielded the phosphine oxide-stabilized phosphoranimine cations [tBu3P= O?PR′2=NSiMe3]+ ([3]+, R′ = Me (d), OCH2CF3 (e)). A mechanism is proposed for the unexpected formation of [4]+ in which the formation of the donor-stabilized adduct [3]+ occurs as the first step.
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