Gas-Phase Structure of the Monomeric Alkylgallium(I) Compound Ga[C(SiMe3)3] and the Electrochemical Behavior of Ga4[C(SiMe3)3]4 and In4[C(SiMe3)3]4 with EPR Evidence for a Ga4R4 Radical Anion
The gallium(I) compd. Ga4[C(SiMe3)3]4 (1) with a tetrahedral Ga4 core in the solid state gives on evapn. the monomeric Ga(I) alkyl Ga[C(SiMe3)3] with the unique structural situation of a Ga atom solely coordinated by one singly bonded carbon ligand. Its mol. structure was detd. now by gas-phase electron diffraction yielding a Ga-C bond length of 206.4(17) pm, similar to that found in the solid state for the tetramer and much longer than in compds. with gallium in the normal oxidn. state of +3. As shown by cyclic voltammetry, 1 and the analogous cluster In4[C(SiMe3)3]4 (2) could both be reversibly reduced at about -2 V vs Fc+/0. Whereas the reduced organoindium tetramer did not exhibit any detectable EPR signals between 4 and 300 K, the gallium analog showed an EPR spectrum compatible with the formulation [(RGa0.75)4].bul.-; i.e. the unpaired electron was delocalized over all four metal centers (a(69Ga) = 1.93 mT, a(71Ga) = 2.45 mT, 4 Ga). [on SciFinder(R)]
%0 Journal Article
%1 Haaland.1996
%A Haaland, Arne
%A Martinsen, Kjell-Gunnar
%A Volden, H. V.
%A Kaim, Wolfgang
%A Waldhoer, Eberhard
%A Uhl, Werner
%A Schuetz, Uwe.
%D 1996
%J Organometallics
%K ESR anion cyclic diffraction formation gallium indium;electron mol monomeric radical silylmethyl silylmethylgallium;silylmethyl structure voltammetry
%N 4
%P 1146--1150
%R 10.1021/OM950755S
%T Gas-Phase Structure of the Monomeric Alkylgallium(I) Compound Ga[C(SiMe3)3] and the Electrochemical Behavior of Ga4[C(SiMe3)3]4 and In4[C(SiMe3)3]4 with EPR Evidence for a Ga4R4 Radical Anion
%V 15
%X The gallium(I) compd. Ga4[C(SiMe3)3]4 (1) with a tetrahedral Ga4 core in the solid state gives on evapn. the monomeric Ga(I) alkyl Ga[C(SiMe3)3] with the unique structural situation of a Ga atom solely coordinated by one singly bonded carbon ligand. Its mol. structure was detd. now by gas-phase electron diffraction yielding a Ga-C bond length of 206.4(17) pm, similar to that found in the solid state for the tetramer and much longer than in compds. with gallium in the normal oxidn. state of +3. As shown by cyclic voltammetry, 1 and the analogous cluster In4[C(SiMe3)3]4 (2) could both be reversibly reduced at about -2 V vs Fc+/0. Whereas the reduced organoindium tetramer did not exhibit any detectable EPR signals between 4 and 300 K, the gallium analog showed an EPR spectrum compatible with the formulation [(RGa0.75)4].bul.-; i.e. the unpaired electron was delocalized over all four metal centers (a(69Ga) = 1.93 mT, a(71Ga) = 2.45 mT, 4 Ga). [on SciFinder(R)]
@article{Haaland.1996,
abstract = {The gallium(I) compd. Ga4[C(SiMe3)3]4 (1) with a tetrahedral Ga4 core in the solid state gives on evapn. the monomeric Ga(I) alkyl Ga[C(SiMe3)3] with the unique structural situation of a Ga atom solely coordinated by one singly bonded carbon ligand. Its mol. structure was detd. now by gas-phase electron diffraction yielding a Ga-C bond length of 206.4(17) pm, similar to that found in the solid state for the tetramer and much longer than in compds. with gallium in the normal oxidn. state of +3. As shown by cyclic voltammetry, 1 and the analogous cluster In4[C(SiMe3)3]4 (2) could both be reversibly reduced at about -2 V vs Fc+/0. Whereas the reduced organoindium tetramer did not exhibit any detectable EPR signals between 4 and 300 K, the gallium analog showed an EPR spectrum compatible with the formulation [(RGa0.75)4].bul.-; i.e. the unpaired electron was delocalized over all four metal centers (a(69Ga) = 1.93 mT, a(71Ga) = 2.45 mT, 4 Ga). [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Haaland, Arne and Martinsen, Kjell-Gunnar and Volden, H. V. and Kaim, Wolfgang and Waldhoer, Eberhard and Uhl, Werner and Schuetz, Uwe.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/20cc8f23fd2d3a08d413b7cbb9a413a3f/huebleriac},
doi = {10.1021/OM950755S},
interhash = {392626e30029f00db3365a7c3a5ed3c3},
intrahash = {0cc8f23fd2d3a08d413b7cbb9a413a3f},
issn = {0276-7333},
journal = {Organometallics},
keywords = {ESR anion cyclic diffraction formation gallium indium;electron mol monomeric radical silylmethyl silylmethylgallium;silylmethyl structure voltammetry},
number = 4,
pages = {1146--1150},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Gas-Phase Structure of the Monomeric Alkylgallium(I) Compound Ga[C(SiMe3)3] and the Electrochemical Behavior of Ga4[C(SiMe3)3]4 and In4[C(SiMe3)3]4 with EPR Evidence for a Ga4R4 Radical Anion},
volume = 15,
year = 1996
}
