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Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
An unsymmetric oxo/imido-bridged germanium-centered singlet diradicaloid
Xinping Wang1, Yang Peng, Marilyn M Olmstead
1Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, USA.
Abstract:
Reaction of the digermyne Ar'GeGeAr' (1) with ONC(6)H(4)-2-CH(3) affords a unique example of an unsymmetric singlet diradicaloid, the oxo/imido-bridged species Ar'Ge(mu-O)(mu-NC(6)H(4)-2-CH(3))GeAr' (2), which was characterized by spectroscopy, X-ray crystallography, and density functional theory computations. The direct reaction of 1 with O(2) to generate the symmetric diradicaloid Ar'Ge(mu(2)-O)(2)GeAr' led to the double-addition product Ar'Ge(mu(2)-O)(2)(eta(1),eta(1):mu(2)-O(2))GeAr' (8), which was also characterized structurally and spectroscopically. Calculations on simple models showed that the HOMO-LUMO energy gap decreases as the imido bridges in MeGe(mu-NH)(2)GeMe are replaced by oxygens, which is consistent with the higher reactivity of Ar'Ge(mu(2)-O)(2)GeAr' toward further O(2) addition.
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