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 degrees C to a tetrameric Ni-I species, [Ni{N(Si...

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Published inAngewandte Chemie International Edition Vol. 54; no. 44; pp. 12914 - 12917
Main Authors Faust, Michelle, Bryan, Aimee M., Mansikkamaki, Akseli, Vasko, Petra, Olmstead, Marilyn M., Tuononen, Heikki M., Grandjean, Fernande, Long, Gary J., Power, Philip P.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 26.10.2015
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
silylamide
nickel
NICKEL(I)
magnetism
REACTIVITY
COBALT(II)
STRUCTURAL-CHARACTERIZATION
CO
steric effects
dispersion effects
AMIDO COMPLEXES
2-COORDINATE
NI
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Summary: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 degrees 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.
Bibliography:Academy of Finland (AKA)
National Science Foundation
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201505518