The Instability of Ni{N(SiMe3)2}2: A Fifty Year Old Transition Metal Silylamide Mystery. Issue 44 (2nd September 2015)

• Record Type: Journal Article
• Authors: Faust, Michelle; Bryan, Aimee M.; Mansikkamäki, Akseli; Vasko, Petra; Olmstead, Marilyn M.; Tuononen, Heikki M.; Grandjean, Fernande; Long, Gary J.; Power, Philip P.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 44(2015)
• Page Start: 12914
• Page End: 12917
• Publication Date: 2015-09-02
• Subjects: dispersion effects -- magnetism -- nickel -- silylamide -- steric effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201505518
• Languages: English
• ISSNs: 1433-7851

Abstract

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.