Oxidation of Carbene-Stabilized Diarsenic: Diarsene Dications and Diarsenic Radical Cations
Journal of the American Chemical Society2013Vol. 135(7), pp. 2486–2488
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M.Y. Abraham, Yuzhong Wang, Yaoming Xie, Robert J. Gilliard, Pingrong Wei, Brian J. Vaccaro, Michael K. Johnson, Henry F. Schaefer, Paul von Ragué Schleyer, Gregory H. Robinson
Abstract
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.
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