Seino Hidetake, Yoshikawa Takanori, Hidai Masanobu, Mizobe Yasushi
Institute of Industrial Science, The University of Tokyo, Japan.
Dalton Trans. 2004 Nov 7(21):3593-600. doi: 10.1039/b409623a. Epub 2004 Sep 29.
Reactions of [TpRh(coe)(MeCN)](; Tp= HB(3,5-dimethylpyrazol-1-yl)(3); coe = cyclooctene) with one equiv. of the organic disulfides, PhSSPh, TolSSTol (Tol = 4-MeC(6)H(4)), PySSPy (Py = 2-pyridyl), and tetraethylthiuram disulfide in THF at room temperature afforded the mononuclear Rh(III) complexes Tp*Rh(SPh)(2)(MeCN), Tp*Rh(STol)(2)(MeCN), Tp*Rh(eta(2)-SPy)(eta(1)-SPy), and Tp*Rh(eta(2)-S(2)CNEt(2))(eta(1)-S(2)CNEt(2)), respectively, via the oxidative addition of the organic disulfides to the Rh(I) center in 1. For the Tp analogue [TpRh(coe)(MeCN)](2, Tp = HB(pyrazol-1-yl)(3)), the reaction with TolSSTol proceeded similarly to give the bis(thiolato) complex TpRh(STol)(2)(MeCN) as a major product but the dinuclear complex TpRh(STol)(micro-STol)(2) was also obtained in low yield. Complex 3 was treated further with the Rh(III) or Ir(III) complexes (Cp*MCl)(2)(micro-Cl)(2) in THF at room temperature, yielding the thiolato-bridged dinuclear complexes [TpRhCl(micro-SPh)(2)MCp*Cl](8a: M = Rh, 8b: M = Ir). Dirhodium complex TpRhCl(micro-STol)(2)RhCp*Cl was obtained similarly from 4 and [(CpRhCl)(2)(micro-Cl)(2)]. Anion metathesis of 8a proceeds only at the Rh atom with the Cp* ligand to yield [TpRhCl(micro-SPh)(2)RhCp(MeCN)]PF(6), when treated with excess KPF(6) in CH(2)Cl(2)-MeCN. The X-ray analyses have been undertaken to determine the detailed structures of 3b, 4, 5, 6, 7, 8a, 9, and 10.
[TpRh(coe)(MeCN)]（；Tp = HB(3,5 - 二甲基吡唑 - 1 - 基)(3)；coe = 环辛烯）与一当量的有机二硫化物PhSSPh、TolSSTol（Tol = 4 - 甲基苯基）、PySSPy（Py = 2 - 吡啶基）以及四乙基秋兰姆二硫化物在室温下于四氢呋喃中反应，分别通过有机二硫化物向1中Rh(I)中心的氧化加成反应，得到单核Rh(III)配合物[TpRh(SPh)(2)(MeCN)]（3a）、[TpRh(STol)(2)(MeCN)]（3b）、[TpRh(η² - SPy)(η¹ - SPy)]（6）以及[TpRh(η² - S₂CNEt₂)(η¹ - S₂CNEt₂)]（7）。对于Tp类似物[TpRh(coe)(MeCN)]（2，Tp = HB(吡唑 - 1 - 基)(3)），与TolSSTol的反应类似，以双(硫醇根)配合物[TpRh(STol)(2)(MeCN)]（4）作为主要产物，但也以低产率得到双核配合物[[TpRh(STol)]₂(μ - STol)₂]（5）。配合物3在室温下于四氢呋喃中进一步与Rh(III)或Ir(III)配合物[(CpMCl)₂(μ - Cl)₂]（Cp = η⁵ - C₅Me₅）反应，生成硫醇根桥联的双核配合物[TpRhCl(μ - SPh)₂MCpCl]（8a：M = Rh，8b：M = Ir）。二铑配合物[TpRhCl(μ - STol)₂RhCpCl]（9）类似地由4和[(CpRhCl)₂(μ - Cl)₂]得到。当在二氯甲烷 - 乙腈中用过量KPF₆处理时，8a的阴离子交换仅在带有Cp配体的Rh原子处发生，生成[TpRhCl(μ - SPh)₂RhCp*(MeCN)][PF₆]（10）。已进行X射线分析以确定3b、4、5、6、7、8a、9和10的详细结构。
