Ligand exchange reactions between copper(II) and nickel(II) chelates of different sulphur and selenium containing ligands. VII. Single-crystal ESR study on the mixed ligand chelate system Ph4As[Cu/Zn(mnt)(Et2dtc)] and crystal and molecular structure of Ph4As[Zn(mnt)(Et2dtc)] |
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| Institution: | 1. University of Utah Department of Civil and Environmental Engineering, Nuclear Engineering Program, Salt Lake City, UT 84112, USA;2. Los Alamos National Laboratory, Los Alamos, NM 87545, USA;3. Pacific Northwest National Laboratory, Richland, WA 99352, USA;4. Lawrence Livermore National Laboratory, 7000 East Ave, Livermore, CA 94550, USA;5. University of Utah Scientific Computing and Imaging Institute, Salt Lake City, UT 84112, USA;6. SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA |
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| Abstract: | The synthesis and crystal and molecular structure of the first zinc(II) mixed ligand chelate containing a dithiolene ligand (maleonitriledithiolate) and N,N- diethyldithiocarbamate are reported. The compound Ph4AsZn(mnt)(Et2dtc)] crystallizes monoclinic, space group P21/c with four molecules in the unit cell; a=17.834(3), b=12.056(2), c=16.171(4) Å, β=93.73(2)°.The coordination geometry of the ZnS4 unit is nearly tetrahedral, with a dihedral angle of 87.6° between the chelate rings. The structure is compared with those of both the patent compounds (Ph4- As)2Zn(mnt)2] and Zn2(Et2dtc)4. Ph4AsZn(mnt)(Et2dtc)] could be used as the host lattice in single- crystal ESR investigations of the planar Cu mixed ligand complex. The rhombic spin-Hamiltonian parameters g and ACu are indicative of a low symmetry of the incorporated Cu(mnt)(Et2dtc)]− complex anions. In order to substantiate the experimental findings about the actual structure of the copper molecules, the principal values of g and ACu were recalculated by means of Extended Hückel MO calculations. However, the calculations performed for the dihedral angles between the ligand planes varying between 0° and 90° suggest that the rotation of the ligands is not larger than 10° |
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