Seidel Wolfram W, Ibarra Arias Maria D, Schaffrath Markus, Jahnke Mareike C, Hepp Alexander, Pape Tania
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 30/36, 48149 Münster, Germany.
Inorg Chem. 2006 Jun 12;45(12):4791-800. doi: 10.1021/ic052178y.
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)}, 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.
通过还原去除相应的双（苄硫基）乙炔配合物Tp'M(CO)2{η2-(BnS)CC(SBn)}中的一个苄基，已对η2-炔-1-硫配合物[Tp'M(CO)2{η2-(BnS)CC(S)}]（Tp' = 氢三（3,5-二甲基吡唑基）硼酸酯；Bn = 苄基；M = Mo、W）的简便合成方法进行了深入研究。提供了中间体[Tp'M(CO)2{η2-(BnS)CC(SBn)}]（M = Mo、W）的实验证据，以及通过分离副产物[Tp'W(CO){C(O)Bn}{η2-(BnS)CC(SBn)}]确定裂解苄基的去向。带有游离末端硫原子的中性η2-炔-1-硫配合物[Tp'M(CO)2{η2-(BnS)CC(S)}]已被确定为与镍(II)和钯(II)形成的同核五核[M'L4]2+配合物中的单齿配体L。将异双金属配合物与游离硫代炔配合物的核磁共振和红外光谱以及循环伏安数据进行比较，揭示了氧化还原活性的η2-CC键合金属中心与硫配位金属离子之间存在强电子耦合。
