The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery

Michelle A. Faust; Aimee M. Bryan; Akseli Mansikkamäki; Petra Vasko; Marilyn M. Olmstead; Heikki M. Tuononen; Fernande Grandjean; Gary J. Long; Philip P. Power

doi:10.1002/anie.201505518

The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery

Michelle A. Faust
, Aimee M. Bryan
, Akseli Mansikkamäki
, Petra Vasko
, Marilyn M. Olmstead
, Heikki M. Tuononen
, Fernande Grandjean
, Gary J. Long
, Philip P. Power

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	American English
Pages (from-to)	12914-12917
Number of pages	4
Journal	Angewandte Chemie International Edition
Volume	54
Issue number	44
DOIs	https://doi.org/10.1002/anie.201505518
State	Published - Oct 1 2015

Keywords

Dispersions
Magnetism
Transition metals
Computational data
Dispersion effect
Dispersion force
Silylamide
Steric effect
Tetrameric
Nickel

Disciplines

Chemistry
Numerical Analysis and Scientific Computing

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10.1002/anie.201505518License: CC BY

https://doi.org/10.1002/anie.201505518

Cite this

Faust, M. A., Bryan, A. M., Mansikkamäki, A., Vasko, P., Olmstead, M. M., Tuononen, H. M., Grandjean, F., Long, G. J., & Power, P. P. (2015). The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery. Angewandte Chemie International Edition, 54(44), 12914-12917. https://doi.org/10.1002/anie.201505518

The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery. / Faust, Michelle A.; Bryan, Aimee M.; Mansikkamäki, Akseli et al.
In: Angewandte Chemie International Edition, Vol. 54, No. 44, 01.10.2015, p. 12914-12917.

Research output: Contribution to journal › Article › peer-review

Faust, MA, Bryan, AM, Mansikkamäki, A, Vasko, P, Olmstead, MM, Tuononen, HM, Grandjean, F , Long, GJ & Power, PP 2015, 'The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery', Angewandte Chemie International Edition, vol. 54, no. 44, pp. 12914-12917. https://doi.org/10.1002/anie.201505518

@article{c6d32425be1547a08433a05ac2116ee2,

title = "The Instability of Ni\{N(SiMe₃)₂\}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery",

abstract = " 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.",

keywords = "Dispersions, Magnetism, Transition metals, Computational data, Dispersion effect, Dispersion force, Silylamide, Steric effect, Tetrameric, Nickel",

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year = "2015",

month = oct,

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doi = "10.1002/anie.201505518",

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T2 - A Fifty Year Old Transition Metal Silylamide Mystery

AU - Faust, Michelle A.

AU - Bryan, Aimee M.

AU - Mansikkamäki, Akseli

AU - Vasko, Petra

AU - Olmstead, Marilyn M.

AU - Tuononen, Heikki M.

AU - Grandjean, Fernande

AU - Long, Gary J.

AU - Power, Philip P.

PY - 2015/10/1

Y1 - 2015/10/1

N2 - 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.

AB - 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.

KW - Dispersions

KW - Magnetism

KW - Transition metals

KW - Computational data

KW - Dispersion effect

KW - Dispersion force

KW - Silylamide

KW - Steric effect

KW - Tetrameric

KW - Nickel

UR - https://scholarsmine.mst.edu/chem_facwork/2490

UR - https://doi.org/10.1002/anie.201505518

U2 - 10.1002/anie.201505518

DO - 10.1002/anie.201505518

M3 - Article

SN - 1521-3773

VL - 54

SP - 12914

EP - 12917

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 44

ER -

The Instability of Ni{N(SiMe₃)₂}₂: A Fifty Year Old Transition Metal Silylamide Mystery: A Fifty Year Old Transition Metal Silylamide Mystery

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