Synthesis and thermal transformations of molecular complexes of bis[tris(trifluoromethyl)germyl]mercury( ii with o-quinones.

Stable molecular complexes of bis[tris(trifluoromethyl)germyl]mercury( II) Hg[(CF)Ge] ( 1) with o-quinones (3,6-di- tert-butylbenzoquinone-1,2 ( 2), 3,6-di- tert-butyl-4,5-dimethoxybenzoquinone-1,2 ( 3), and 1,4,5,7-tetra- tert-butyldibenzo[1,4]dioxin-2,3-dione ( 4)) have been synthesized and characterized by elemental analysis and IR and electronic absorption spectroscopies. Depending on the ratio between the starting reactants, the reactions of o-quinones with 1 gave complexes of the composition RHg · Q ( 5, 7, 9) or RHg · Q ( 6, 8, 10), where Q= 2 ( 5, 6), 3 ( 7, 8), 4 ( 9, 10); R=Ge(CF). According to the spectral data, the molecule of o-quinone in RHg · Q acts as a neutral ligand, whereas the second molecule of o-quinone in RHg · Q is not coordinated to 1. It has been found by ESR that thermolysis of polycrystalline samples of complexes 6 and 10 involves intermediate formation of radical pairs and finally yields paramagnetic o-semiquinone complexes, SQGe(CF), which are typical products of one-electron oxidation of Organometallic compounds by o-quinones. [ABSTRACT FROM AUTHOR]