Fernández P, Sousa-Pedrares A, Romero J, García-Vázquez J A, Sousa A, Pérez-Lourido P
Departamento de Química Inorgánica, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain.
Inorg Chem. 2008 Mar 17;47(6):2121-32. doi: 10.1021/ic7005925. Epub 2008 Feb 14.
Neutral zinc, cadmium, mercury(II), and ethylmercury(II) complexes of a series of phosphinothiol ligands, PhnP(C6H3(SH-2)(R-3))3-n (n = 1, 2; R = H, SiMe3) have been synthesized and characterized by IR and NMR ((1)H, (13)C, and (31)P) spectroscopy, FAB mass spectrometry, and X-ray structural analysis. The compounds [Zn{PhP(C6H4S-2)2}] (1) and [Cd{Ph2PC6H4S-2}2] (2) have been synthesized by electrochemical oxidation of anodic metal (zinc or cadmium) in an acetonitrile solution of the appropriate ligand. The presence of pyridine in the electrolytic cell affords the mixed complexes [Zn{PhP(C6H4S-2)2}(py)] (3) and [Cd{PhP(C6H4S-2)2}(py)] (4). [Hg{Ph2PC6H4S-2}2] (5) and [Hg{Ph2PC6H3(S-2)(SiMe3-3)}2] (6) were obtained by the addition of the appropriate ligand to a solution of mercury(II) acetate in methanol in the presence of triethylamine. [EtHg{Ph2PC6H4S-2}] (7), [EtHg{Ph2P(O)C6H3(S-2)(SiMe3-3)}] (8), [{EtHg}2{PhP(C6H4S-2)2}] (9), and [{EtHg}2{PhP(C6H3(S-2)(SiMe3-3))2}] (10) were obtained by reaction of ethylmercury(II) chloride with the corresponding ligand in methanol. In addition, in the reactions of EtHgCl with Ph2PC6H4SH-2 and with the potentially tridentate ligand PhP(C6H3(SH-2)(SiMe3-3)) 2, cleavage of the Hg-C bond was observed with the formation of [Hg{Ph2PC6H4S-2}2] (5) and [Hg(EtHg) 2{PhP(O)(C6H3(S-2)(SiMe3-3))2}2] (11), respectively, and the corresponding hydrocarbon. The crystal structures of [Zn3{PhP(C6H4S-2)2}2{PhP(O)(C6H4S-2)2}] (1*), [Cd2{Ph2PC6H4S-2}3{Ph2P(O)C6H4S-2}] (2*), 3, 5, 6, [EtHg{Ph2P(O)C6H4S-2}] (7*), 8, 9, [{EtHg}2{PhP(O)(C6H3(S-2)(SiMe3-3))2}] (10*), and 11 are discussed. The molecular structures of 1, 2, 4, 7, and 10 have also been studied by means of density functional theory (DFT) calculations.
合成了一系列膦硫醇配体PhnP(C6H3(SH-2)(R-3))3-n（n = 1, 2；R = H, SiMe3）的中性锌、镉、汞（II）和乙基汞（II）配合物，并通过红外光谱和核磁共振（（1）H、（13）C和（31）P）光谱、快原子轰击质谱和X射线结构分析对其进行了表征。化合物[Zn{PhP(C6H4S-2)2}]（1）和[Cd{Ph2PC6H4S-2}2]（2）是通过在适当配体的乙腈溶液中对阳极金属（锌或镉）进行电化学氧化合成的。电解池中存在吡啶时可得到混合配合物[Zn{PhP(C6H4S-2)2}(py)]（3）和[Cd{PhP(C6H4S-2)2}(py)]（4）。[Hg{Ph2PC6H4S-2}2]（5）和[Hg{Ph2PC6H3(S-2)(SiMe3-3)}2]（6）是在三乙胺存在下，将适当的配体加入到甲醇中的醋酸汞（II）溶液中得到的。[EtHg{Ph2PC6H4S-2}]（7）、[EtHg{Ph2P(O)C6H3(S-2)(SiMe3-3)}]（8）、[{EtHg}2{PhP(C6H4S-2)2}]（9）和[{EtHg}2{PhP(C6H3(S-2)(SiMe3-3))2}]（10）是通过氯化乙基汞（II）与相应配体在甲醇中反应得到的。此外，在EtHgCl与Ph2PC6H4SH-2以及与潜在的三齿配体PhP(C6H3(SH-2)(SiMe3-3))2的反应中，观察到Hg-C键的断裂，分别形成了[Hg{Ph2PC6H4S-2}2]（5）和[Hg(EtHg)2{PhP(O)(C6H3(S-2)(SiMe3-3))2}2]（11）以及相应的烃。讨论了[Zn3{PhP(C6H4S-2)2}2{PhP(O)(C6H4S-2)2}]（1*）、[Cd2{Ph2PC6H4S-2}3{Ph2P(O)C6H4S-2}]（2*）、3、5、6、[EtHg{Ph2P(O)C6H4S-2}]（7*）、8、9、[{EtHg}2{PhP(O)(C6H3(S-2)(SiMe3-3))2}]（10*）和11的晶体结构。还通过密度泛函理论（DFT）计算研究了1、2、4、7和10的分子结构。
