Abstract
Theredox chemistry of [Cp"'Ni(& eta;(3)-As-3)] (A), an end-deck cyclo-As-3 complex, is explored in terms of systematically accessinga series of Ni2As3 triple-decker compounds.While oxidation of A affords the cationic complex [{Cp"'Ni}(2)(& mu;,& eta;(3:3)-As-3)][FAl] (1, [FAl](-) = [FAl{O(1-C6F5)C6F10}(3)](-)), reduction of A yields the anionic [K@crypt][{Cp"'Ni}(2)(& mu;,& eta;(3:3)-As-3)] (2, ...
Abstract
Theredox chemistry of [Cp"'Ni(& eta;(3)-As-3)] (A), an end-deck cyclo-As-3 complex, is explored in terms of systematically accessinga series of Ni2As3 triple-decker compounds.While oxidation of A affords the cationic complex [{Cp"'Ni}(2)(& mu;,& eta;(3:3)-As-3)][FAl] (1, [FAl](-) = [FAl{O(1-C6F5)C6F10}(3)](-)), reduction of A yields the anionic [K@crypt][{Cp"'Ni}(2)(& mu;,& eta;(3:3)-As-3)] (2, crypt = [2.2.2]-cryptand). One-electron reduction of 1 and one-electron oxidation of 2 yield the neutral compound[{Cp"'Ni}(2)(& mu;,& eta;(3:3)-As-3)] (3), representing the missing link between 1 and 2, which is corroborated electrochemically.The cyclo-As-3 ligand in 2 undergoes bond weakening and splitting of one As-As bondupon stepwise oxidation to 3 and 1, finallydisplaying an allylic As-3 ligand. In-depth experimentalstudies shed light onto the reaction pathway of the oxidation of A, and additional DFT computations give insight into the electronicstructure of the obtained complexes.
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