The Instability of Ni{N(SiMe3 )2 }2 : A Fifty Year Old Transition Metal Silylamide Mystery.
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.
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616 (USA).
Michelle
M
Faust
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616 (USA).
Aimee M
AM
Bryan
Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä (Finland).
Akseli
A
Mansikkamäki
Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä (Finland).
Petra
P
Vasko
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616 (USA).
Marilyn M
MM
Olmstead
Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä (Finland). heikki.m.tuononen@jyu.fi.
Heikki M
HM
Tuononen
Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO 65409-0010 (USA).
Fernande
F
Grandjean
Department of Chemistry, Missouri University of Science and Technology, University of Missouri, Rolla, MO 65409-0010 (USA).
Gary J
GJ
Long
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616 (USA). pppower@ucdavis.edu.
Philip P
PP
Power
dispersion effects; magnetism; nickel; silylamide; steric effects