Reversible addition of tin(II) amides to nitriles

Dalton Trans. 2022 Feb 1;51(5):1879-1887. doi: 10.1039/d1dt04060j.

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.