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Synthesis and characterization of zinc and cadmium compounds with arenephosphinothiol ligands. Crystal and molecular structures of [Cd{sub 2}{l{underscore}brace}2-(Ph{sub 2}PO)C{sub 6}H{sub 4}S{r{underscore}brace}{sub 4}], [Zn{l{underscore}brace}2-(Ph{sub 2}P)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}], [Cd{l{underscore}brace}2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}(CH{sub 3}OH)], and [Zn{l{underscore}brace}PhPO(C{sub 6}H{sub 4}S-2){sub 2}{r{underscore}brace}(bipy)]

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic981405b· OSTI ID:20003191

The electrochemical oxidation of a metallic anode (zinc or cadmium) in an acetonitrile solution of a series of arenephosphinothiol ligands, 2-(Ph{sub 2}P)C{sub 6}H{sub 4}SH, 2-(Ph{sub 2}P)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH, 2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH, and PhP-(C{sub 6}H{sub 4}SH-2){sub 2} [abbreviated RP-(SH){sub x}, x = 1 or 2], affords [M(RP-S){sub 2}] and [M(RP-S{sub 2})], M = Zn, Cd. Adducts of several of these compounds with 1,10-phenanthroline and 2,2{prime}-bipyridine have also been obtained by addition of these coligands to the electrolysis phase. The compounds obtained have been characterized by microanalysis, IR, UV-visible, FAB spectrometry and {sup 1}H, {sup 31}P NMR spectroscopic studies. The compounds [Cd{sub 2}{l{underscore}brace}2-(Ph{sub 2}PO)-C{sub 6}H{sub 4}S{r{underscore}brace}{sub 4}]CH{sub 3}CN (1), [Zn{l{underscore}brace}2-(Ph{sub 2}P)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}] (2), [Cd{l{underscore}brace}2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}S{r{underscore}brace}{sub 2}(CH{sub 3}OH)] (3), and [Zn{l{underscore}brace}PhPO(C{sub 6}H{sub 4}S-2){sub 2}{r{underscore}brace}(bipy)] (4), have been also characterized by single-crystal X-ray diffraction. Compound 1 is binuclear with a {l{underscore}brace}Cd{sub 2}S{sub 2}{r{underscore}brace} core and distorted trigonal bipyramidal {l{underscore}brace}CdO{sub 2}S{sub 3}{r{underscore}brace} geometry about the Cd sites. Compounds 2, 3, and 4 are mononuclear with distorted tetrahedral {l{underscore}brace}ZnP{sub 2}S{sub 2}{r{underscore}brace}, distorted square pyramidal {l{underscore}brace}CdO{sub 3}S{sub 2}{r{underscore}brace}, and distorted trigonal bipyramidal {l{underscore}brace}ZnON{sub 2}S{sub 2}{r{underscore}brace} geometries, respectively.

Research Organization:
Univ. de Santiago de Compostela (ES)
Sponsoring Organization:
Xunta de Galicia; Department of Energy
DOE Contract Number:
FG02-99ER62791
OSTI ID:
20003191
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 38; ISSN INOCAJ
Country of Publication:
United States
Language:
English