The Instability of Ni{N(SiMe3)2}2: A Fifty Year Old Transition Metal Silylamide Mystery. Issue 44 (2nd September 2015) - Faust, Michelle
Abstract: The characterization of the unstable Ni II bis(silylamide) Ni{N(SiMe3 )2 }2 (1 ), its THF complex Ni{N(SiMe3 )2 }2 (THF) (2 ), and the stable bis(pyridine) derivative trans‐Ni{N(SiMe3 )2 }2 (py)2 (3 ), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric Ni I species, [Ni{N(SiMe3 )2 }]4 (4 ), also obtainable from LiN(SiMe3 )2 and NiCl2 (DME). Experimental and computational data indicate that the instability of 1 is likely due to ease of reduction of Ni II to Ni I and the stabilization of 4 through dispersion forces. Abstract : The singular instability of Ni{N(SiMe3 )2 }2, one of the original transition metal silylamides of Bürger and Wannagat, was re‐investigated: it likely results from its tendency to undergo autoreduction into the dispersion force stabilized Ni I tetramer [Ni{N(SiMe3 )2 }]4 (see picture; Si light blue, N dark blue, Ni green), the first neutral homoleptic Ni I amide.