Oxidation of carbene-stabilized diarsenic: diarsene dications and diarsenic radical cations.
Oxidation of carbene-stabilized diarsenic, L:As-As:L [L: = :C{N(2,6-(i)Pr(2)C(6)H(3))CH}(2)] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:As═As:L](2+)([GaCl(4)](-))(2) (2(2+)[GaCl(4)](2)), while oxidation of 1 with GaCl(3) in a 1:2 ratio in Et(2)O yields the monocationic diarsenic radical complex [L:AsAs:L](•+)[GaCl(4)](-) (2(•+)[GaCl(4)]). Strikingly, complex 2(•+) is the first arsenic radical to be structurally characterized in the solid state. The nature of the bonding in these complexes was probed computationally and spectroscopically.
Department of Chemistry and the Center for Computational Chemistry, The University of Georgia, Athens, Georgia 30602-2556, USA.
Mariham Y
MY
Abraham
Yuzhong
Y
Wang
Yaoming
Y
Xie
Robert J
RJ
Gilliard
Pingrong
P
Wei
Brian J
BJ
Vaccaro
Michael K
MK
Johnson
Henry F
HF
Schaefer
Paul V R
PV
Schleyer
Gregory H
GH
Robinson