Oxidation of Carbene-Stabilized Diarsenic: Diarsene Dications and Diarsenic Radical Cations

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• 作者：Mariham Y. Abraham ; Yuzhong Wang ; Yaoming Xie ; Robert J. Gilliard ; Jr. ; Pingrong Wei ; Brian J. Vaccaro ; Michael K. Johnson ; Henry F. Schaefer ; III ; Paul v. R. Schleyer ; Gregory H. Robinson
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：February 20, 2013
• 年：2013
• 卷：135
• 期：7
• 页码：2486-2488
• 全文大小：262K
• 年卷期：v.135,no.7(February 20, 2013)
• ISSN：1520-5126

文摘

Oxidation of carbene-stabilized diarsenic, L:As鈥揂s:L [L: = :C{N(2,6-ⁱPr₂C₆H₃)CH}₂] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:As鈺怉s:L]²⁺([GaCl₄]^{鈭?/sup>)₂ (22+[GaCl₄]₂), while oxidation of 1 with GaCl₃ in a 1:2 ratio in Et₂O yields the monocationic diarsenic radical complex [L:AsAs:L]鈥?[GaCl₄]鈭?/sup> (2鈥?[GaCl₄]). Strikingly, complex 2鈥? 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.}