Abstract
[Cu(MTQ)(PPh3)2](BF4) (1, MTQ = 8-methylthioquinoline) was prepd. and characterized by x-ray crystallog. 1 Exhibits distorted tetrahedral coordination at the copper(I) center. One of two crystallog. independent mols. found in the unit cell exhibits a more pronounced inclination towards a (3+1) coordination arrangement. In comparison to the analogous complex with the related imine/thioether chelate ligand 1-methyl-2-(methylthiomethyl)-1H-benzimidazole, [Cu(MTQ)(PPh3)2]+ shows stronger bonding of CuI to S and weaker interaction with N. With 3,5-di-tert-butyl-o-semiquinone as co-ligand instead of two PPh3 ligands a valence-tautomer equil. situation involving the copper(II)-catecholate state can be obsd. by EPR spectroscopy, showing an unusually large isotropic 63,65Cu hyperfine coupling of 2.1 mT and an atypically small isotropic g value of 1.975. [on SciFinder(R)]
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