Do S,S′-coordinated o-dithiobenzosemiquinonate(1-) radicals exist in coordination compounds?: The [AuIII(1,2-C6H4S2)2]1-/0 couple

被引:93
作者
Ray, K
Weyhermuller, T
Goossens, A
Crajé, MWJ
Wieghardt, K
机构
[1] Max Planck Inst Strahlenchem, D-45470 Mulheim, Germany
[2] Leiden Univ, Kamerlingh Onnes Lab, NL-2300 RA Leiden, Netherlands
[3] Delft Univ Technol, Interfac Reactor Inst, NL-2629 JB Delft, Netherlands
关键词
D O I
10.1021/ic0207092
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The square planar, light-green, diamagnetic complex [N(n-Bu)(4)][Au-III(Lt-Bu)(2)] (1) reacts with iodine in acetone affording the neutral paramagnetic species [Au(Lt-Bu)(2)] (1a) (S = 1/2) where H-2[Lt-Bu] represents the ligand 3,5-di-tert-butyl-1,2-benzenedithiol. The corresponding complexes containing the unsubstituted ligand H-2[L], 1,2-benzenedithiol, namely [N(n-Bu)(3)H][Au(L)(2)] (2) and [Au(L)(2)] (2a), have also been prepared and characterized by X-ray crystallography; the structure of the latter has been reported in ref 10. Au-197 Mossbauer spectra of 1 and 1a clearly show that the one-electron oxidation is ligand-centered and does not involve the formation of Au(IV) (d(7)). The spectroscopic features of the ligand mixed-valent species la were determined by UV-vis, EPR, and IR spectroscopy which allows the detection of S,S-coordinated 1,2-dithiobenzosemiquinonate(1-) radicals in coordination compounds.
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页码:4082 / 4087
页数:6
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