American Chemical Society
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Donor-Stabilized Cations and Imine Transfer from N-Silylphosphoranimines

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journal contribution
posted on 2004-03-03, 00:00 authored by Eric Rivard, Keith Huynh, Alan J. Lough, Ian Manners
A series of donor-stabilized N-silylphosphoranimine salts [DMAP·PCl2NSiMe3]+X- (DMAP = 4-(dimethylamino)pyridine) were prepared by the reaction of Cl3PNSiMe3 with DMAP in the presence of silver salts AgX (X = OSO2CF3, BF4, and SbF6). Repeating the reaction in the absence of AgX gave the chloride salt [DMAP·PCl2NSiMe3]Cl which has been shown to be in equilibrium with free DMAP and Cl3PNSiMe3. Attempts to stabilize a N-silylphosphoranimine cation with phosphine donors led to unexpected imine transfer chemistry. For example, Cl3PNSiMe3 reacts with phosphines, R3P (R = nBu and Ph), to produce the metathesis products PCl3 and R3PNSiMe3 which subsequently react together to afford the N-phosphinophosphoranimines R3PN−PCl2 and ClSiMe3 as a byproduct.