Abstract
A new mixed valence copper complex Cu(II)(Me(5)dien)Cl(2)(Cu(I)Cl) (2) was obtained from the reaction of CuCl with Cu(II)(Me(5)dien)Cl(2) (1) in acetonitrile. The structures of 1 and 2 have been determined by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 8.374(5) Å, b = 17.155(3) Å, c = 23.806(5) Å, beta = 94.40(4) degrees, Z = 8, and V = 3398(1) Å(3) while compound 2 crystallizes in orthorhombic space group Pbcn with a = 14.71(1) Å, b = 16.06(2) Å, c = 13.38(1) Å, Z = 8, and V = 3159(5) Å. The Cu(II)(Me(5)dien)Cl(2) unit in both compounds has a similar distorted square-pyramidal geometry. The Cu(I)Cl moiety in 2 is attached to the Cu(II) unit via two bridging chlorine atoms and has a distorted trigonal planar geometry. UV-vis and EPR spectroscopic studies and molecular orbital calculations established the presence of significant perturbation of the Cu(I)Cl unit to the electronic structure of the Cu(II) ion in compound 2.
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