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Rivard E, Huynh K, Lough AJ, Manners I: Donor-stabilized cations and imine transfer from N-silylphosphoranimines. J Am Chem Soc. 2004 Mar 3;126(8):2286-7.
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. |
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