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Issue 5, 1987
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A structural comparison of bis(quinoxaline-2,3-dithiolato)cuprate complexes

Abstract

The crystal structures, u.v.–visible spectra, and electrochemical properties of [Cu(qdt)2]2– and [Cu(qdt)2](qdt = quinoxaline-2,3-dithiolate) are reported. The compound [PPh4]2[Cu(qdt)2] crystallizes in space group P21/c with a= 9.9320(4), b= 23.8217(10), c= 11.9178(5)Å, β= 95.075(5)°, and Z= 2; [PPh4][Cu(qdt)2] crystallizes in space group P2/n with a= 23.709(2), b= 7.192(1), c= 24.188(2)Å, β= 119.170(6)°, and Z= 4. In both anions the CuS4 moiety is essentially planar, with the mean Cu–S bond length in [Cu(qdt)2][2.187(1)Å] being significantly shorter than that in [Cu(qdt)2]2–[2.260(1)Å], consistent with the unpaired electron of the latter complex occupying an orbital which is antibonding with respect to the Cu–S σ bonds. The [Cu(qdt)2]–[Cu(qdt)2]2– couple is electrochemically reversible with E½=–0.18 V vs. saturated calomel electrode in dimethylformamide; a quasi-reversible process with E½=–1.28 V observed in this solvent is attributed to the [Cu(qdt)2]2––[Cu(qdt)2]3– couple.

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Article information


J. Chem. Soc., Dalton Trans., 1987, 1083-1087
Article type
Paper

A structural comparison of bis(quinoxaline-2,3-dithiolato)cuprate complexes

S. Boyde, C. D. Garner and W. Clegg, J. Chem. Soc., Dalton Trans., 1987, 1083
DOI: 10.1039/DT9870001083

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