CHARGE-TRANSFER PHOTOCHEMISTRY OF BIS(DIETHYLDITHIOCARBAMATO)COPPER(II) AND BIS(DIISOPROPYLDITHIOPHOSPHATO)COPPER(II) COMPLEXES

被引:35
作者
JELIAZKOVA, BG [1 ]
YORDANOV, ND [1 ]
机构
[1] BULGARIAN ACAD SCI,INST KINET & CATALYSIS,BU-1113 SOFIA,BULGARIA
关键词
D O I
10.1016/S0020-1693(00)81658-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The photochemistry of bis(diethyldithiocarbamato)copper(II) and bis(diisopropyldithiophosphato)copper(II) complexes characterized by strongly allowed ligand to metal charge transfer transition in the visible spectra is reported. The reaction from the lowest LMCT state is reduction of Cu(II) to Cu(I) proceeding via an intramolecular electron transfer from an equatorially bonded S atom of the ligand to copper(II). Both complexes show solvent independent photochemistry when irradiated in acetone, toluene, CHCl3 and CCl4. UV irradiation of Cu(dtC)2 in mixed chlorohydrocarbon-ethanol solvents gives rise to Cu(II)(dtc)Cl with equatorially coordinated chloride ion as an intermediate and CuCl2 as a final reaction product. The photoproduct of the dithiophosphate complex is partially reconverted into the initial Cu(II)(dtp)2 by thermal reaction. These assignments are supported by EPR data and by UV-Vis spectra of the complexes.
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页码:201 / 204
页数:4
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