Molybdenum and tungsten eta2-alkyne-1-thio complexes acting as sulfur donors in homoleptic Werner type complexes with nickel(II) and palladium(II).
Molybdenum and tungsten eta2-alkyne-1-thio complexes acting as sulfur donors in homoleptic Werner type complexes with nickel(II) and palladium(II).
复制标题
钼和钨 eta2-alkyne-1-thio 配合物在与镍 (II) 和钯 (II) 的均配 Werner 型配合物中充当硫供体。
DOI：
10.1021/ic052178y
复制
发表时间：
2006
影响因子：
4.6
通讯作者：
T. Pape
中科院分区：
文献类型：
--
作者：
W. Seidel;Maria D Ibarra Arias;M. Schaffrath;Mareike C. Jahnke;A. Hepp;T. Pape
eta2-炔-1-硫配合物[Tp m (CO)2{eta2-(BnS)CC(S)}] (Tp′=水（3,5-二甲基吡唑基）硼酸酯；Bn =苄基；通过还原去除相应的双（苄基硫）乙炔配合物[Tp M(CO)2{eta2-(BnS)CC（SBn)}]（PF6）中的一个苄基，对M = Mo， W）进行了深入的研究。实验证明了中间体[Tp M(CO)2{eta2-(BnS)CC(SBn)}] （M = Mo， W）和分离副产物[Tp'W(CO){C(O)Bn}{eta2-(BnS)CC(SBn)}]裂解苯基的结局。中性的eta2-炔-1-硫配合物[Tp M(CO)2{eta2-(BnS)CC(S)}]在与镍（II）和钯（II）的同色五核[M'L4]2+配合物中被确定为单齿配体L。杂双金属配合物与游离硫代炔配合物的核磁共振、红外光谱和环伏安数据的比较表明，具有氧化还原活性的et_2 - cc键合金属中心与硫配位金属离子之间存在很强的电子耦合。
Facile access to the eta2-alkyne-1-thio complexes [Tp'M(CO)2{eta2-(BnS)CC(S)}] (Tp' = hydrotris(3,5-dimethylpyrazolyl)borate; Bn = benzyl; M = Mo, W) by reductive removal of one benzyl group in the corresponding bis(benzylthio)acetylene complexes, [Tp'M(CO)2{eta2-(BnS)CC(SBn)}](PF6), has been thoroughly investigated. Experimental evidence of the intermediates, [Tp'M(CO)2{eta2-(BnS)CC(SBn)}] (M = Mo, W), and the fate of the cleaved benzyl group by isolation of the byproduct, [Tp'W(CO){C(O)Bn}{eta2-(BnS)CC(SBn)}], is provided. Neutral eta2-alkyne-1-thio complexes [Tp'M(CO)2{eta2-(BnS)CC(S)}] bearing a free terminal sulfur atom have been established as monodentate ligands L in homoleptic pentanuclear [M'L4]2+ complexes with nickel(II) and palladium(II). Comparison of the NMR and IR spectroscopic as well as cyclovoltammetric data of the heterobimetallic complexes with the free thio-alkyne complexes reveals a strong electronic coupling of the redox-active eta2-CC-bound metal centers and the sulfur-coordinated metal ion.