Reversible addition of tin(ii) amides to nitriles

Abstract

Lappert's stannylene (Sn[N(SiMe₃)₂]₂) has been reacted with various nitriles, dinitriles and trinitriles with the formation of heteroleptic amidotin(II) amidinates of the general formulae [RC(NSiMe₃)₂]SnN(SiMe₃)₂, R′{[C(NSiMe₃)₂]SnN(SiMe₃)₂}₂ and R′′{[C(NSiMe₃)₂]SnN(SiMe₃)₂}₃, where R = Ph (1), 2-(CN)-C₆H₄ (2), 3-(CN)-C₆H₄ (3); R′ = 1,3-C₆H₄ (4), 1,4-C₆H₄ (5) and R′′ = 1,3,5-C₆H₃ (6). The reactions of amidotin(II) benzamidinate 1 with an excess of benzonitrile proceed to homoleptic tin(II) bis(benzamidinate) [PhC(NSiMe₃)₂]₂Sn, which reversibly eliminates benzonitrile and 1 when warmed. The premise of reversibility has been supported by a multinuclear time-dependent NMR study and a theoretical (DFT) description. On the other hand, magnesium(II) bis(benzamidinate) [PhC(NSiMe₃)₂]₂Mg (8) and lanthanum(II) tris(benzamidinate) [PhC(NSiMe₃)₂]₃La (7) have been synthesised from appropriate metal hexamethyldisilazides and benzonitrile.