J. K. Money, J. Huffman, G. Christou
Sep 1, 1985
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0
Influential Citations
43
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Journal
Inorganic Chemistry
Abstract
The synthesis, structure, and properties of vanadium(IV) complexes with the ethane-1,2-dithiolate ligand (edt/sup 2 -/) are described. (NMe/sub 4/)Na(VO(edt)/sub 2/) x 2EtOH crystallizes in monoclinic space group P2/sub 1//n with unit cell parameters (at ca. -159/sup 0/C) a = 21.312 (5) A, b = 10.906 (2) A, c = 9.381 (1) A, ..beta.. = 92.77 (1)/sup 0/, and Z = 4. The vanadium is in a square-pyramidal coordination geometry with the multiply bonded oxygen at the apex (V-O = 1.625 (2) A) and four ligand sulfur atoms in the base. The anion, cations, and solvent molecules pack into discrete units of C/sub 2h/ symmetry. (VO(edt)/sub 2/)/sup 2 -/ was cleanly converted into (VS(edt)/sub 2/)/sup 2/)/sup -/ with hexamethyldisilthiane, (Me/sub 3/Si)/sub 2/S. (PPh/sub 4/)Na(VS(edt)/sub 2/) x xEt/sub 2/O crystallizes in triclinic space group P1 with unit cell parameters (at ca. -160/sup 0/C) a = 17.201 (5) A, b = 10.983 (3) A, c = 9.919 (3) A, ..cap alpha.. = 65.84 (1)/sup 0/, ..beta.. = 106.63 (1)/sup 0/ ..gamma.. = 93.32 (2)/sup 0/, and Z = 2. The anion is isostructural with (VO(edt)/sub 2/)/sup 2 -/ except for the presence of the apical sulfur (V-S = 2.087 (1) A). The anion,more » cations, and solvent molecules again pack into discrete dimers, but of a different structure of D/sub 2h/ symmetry. This is only the second example of a structurally characterized species containing the V=S/sup 2 +/ moiety. Infrared, electrochemical, and UV/visible studies of the two complexes are described. 32 references, 4 figures, 4 tables.« less