title: An unsymmetric oxo/imido-bridged germanium-centered singlet diradicaloid.
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.
authors.affiliation: Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, USA.
authors.forename: Xinping
authors.initials: X
authors.lastname: Wang
authors.forename: Yang
authors.initials: Y
authors.lastname: Peng
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.forename: James C
authors.initials: JC
authors.lastname: Fettinger
authors.forename: Philip P
authors.initials: PP
authors.lastname: Power