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The Instability of Ni{N(SiMe 3 ) 2 } 2 : A Fifty Year Old Transition Metal Silylamide Mystery
Author(s) -
Faust Michelle,
Bryan Aimee M.,
Mansikkamäki Akseli,
Vasko Petra,
Olmstead Marilyn M.,
Tuon Heikki M.,
Grandjean Fernande,
Long Gary J.,
Power Philip P.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201505518
Subject(s) - transition metal , chemistry , pyridine , metal , instability , derivative (finance) , nickel , stereochemistry , medicinal chemistry , crystallography , physics , organic chemistry , catalysis , mechanics , financial economics , economics
The characterization of the unstable Ni II bis(silylamide) Ni{N(SiMe 3 ) 2 } 2 ( 1 ), its THF complex Ni{N(SiMe 3 ) 2 } 2 (THF) ( 2 ), and the stable bis(pyridine) derivative trans‐Ni{N(SiMe 3 ) 2 } 2 (py) 2 ( 3 ), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric Ni I species, [Ni{N(SiMe 3 ) 2 }] 4 ( 4 ), also obtainable from LiN(SiMe 3 ) 2 and NiCl 2 (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.