Seino Hidetake, Kaneko Tetsuhide, Fujii Shunpei, Hidai Masanobu, Mizobe Yasushi
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan, and Department of Materials Science and Technology, Faculty of Industrial Science and Technology, Tokyo University of Science, Noda, Chiba 278-8510, Japan.
Inorg Chem. 2003 Jul 28;42(15):4585-96. doi: 10.1021/ic030129k.
Reactions of a dirhenium tetra(sulfido) complex PPh(4)[ReS(L)(mu-S)(2)ReS(L)] (L = S(2)C(2)(SiMe(3))(2)) with a series of group 8-11 metal complexes in MeCN at room temperature afforded either the cubane-type clusters [M(2)(ReL)(2)(mu(3)-S)(4)] (M = CpRu (2), PtMe(3), Cu(PPh(3)) (4); Cp = eta(5)-C(5)Me(5)) or the incomplete cubane-type clusters [M(ReL)(2)(mu(3)-S)(mu(2)-S)(3)] (M = (eta(6)-C(6)HMe(5))Ru (5), CpRh (6), CpIr (7)), depending on the nature of the metal complexes added. It has also been disclosed that the latter incomplete cubane-type clusters can serve as the good precursors to the trimetallic cubane-type clusters still poorly precedented. Thus, treatment of 5-7 with a range of metal complexes in THF at room temperature resulted in the formation of novel trimetallic cubane-type clusters, including the neutral clusters [[(eta(6)-C(6)HMe(5))Ru]W(CO)(3)(2)(mu(3)-S)(4)], [(CpM)W(CO)(3)(2)(mu(3)-S)(4)] (M = Rh, Ir), [(CpIr)Mo(CO)(3)(2)(mu(3)-S)(4)], [[(eta(6)-C(6)HMe(5))Ru]Pd(PPh(3))(2)(mu(3)-S)(4)], and [(CpIr)Pd(PPh(3))(2)(mu(3)-S)(4)] (13) along with the cationic clusters [(CpIr)(CpRu)(ReL)(2)(mu(3)-S)(4)][PF(6)] (14) and [(CpIr)Rh(cod)(2)(mu(3)-S)(4)][PF(6)] (cod = 1,5-cyclooctadiene). The X-ray analyses have been carried out for 2, 4, 7, 13, and the SbF(6) analogue of 14 (14') to confirm their bimetallic cubane-type, bimetallic incomplete cubane-type, or trimetallic cubane-type structures. Fluxional behavior of the incomplete cubane-type and trimetallic cubane-type clusters in solutions has been demonstrated by the variable-temperature (1)H NMR studies, which is ascribable to both the metal-metal bond migration in the cluster cores and the pseudorotation of the dithiolene ligand bonded to the square pyramidal Re centers, where the temperatures at which these processes proceed have been found to depend upon the nature of the metal centers included in the cluster cores.
二铼四（硫代）配合物PPh(4)[ReS(L)(μ-S)(2)ReS(L)]（L = S(2)C(2)(SiMe(3))(2)）与一系列第8 - 11族金属配合物在室温下于乙腈中反应，根据所添加金属配合物的性质，得到了立方烷型簇合物[M(2)(ReL)(2)(μ(3)-S)(4)]（M = CpRu (2)、PtMe(3)、Cu(PPh(3)) (4)；Cp = η(5)-C(5)Me(5)）或不完全立方烷型簇合物[M(ReL)(2)(μ(3)-S)(μ(2)-S)(3)]（M = (η(6)-C(6)HMe(5))Ru (5)、CpRh (6)、CpIr (7)）。还已揭示，后一种不完全立方烷型簇合物可作为制备仍鲜有先例的三金属立方烷型簇合物的良好前体。因此，在室温下于四氢呋喃中用一系列金属配合物处理5 - 7，导致形成了新型三金属立方烷型簇合物，包括中性簇合物[[(η(6)-C(6)HMe(5))Ru]W(CO)(3)(2)(μ(3)-S)(4)]、[(CpM)W(CO)(3)(2)(μ(3)-S)(4)]（M = Rh、Ir）、[(CpIr)Mo(CO)(3)(2)(μ(3)-S)(4)]、[[(η(6)-C(6)HMe(5))Ru]Pd(PPh(3))(2)(μ(3)-S)(4)]以及[(CpIr)Pd(PPh(3))(2)(μ(3)-S)(4)] (13)，以及阳离子簇合物[(CpIr)(CpRu)(ReL)(2)(μ(3)-S)(4)][PF(6)] (l4)和[(CpIr)Rh(cod)(2)(μ(3)-S)(4)][PF(6)]（cod = 1,5 - 环辛二烯）。已对2、4、7、13以及14的SbF(6)类似物（14'）进行了X射线分析，以确认它们的双金属立方烷型、双金属不完全立方烷型或三金属立方烷型结构。通过变温(1)H NMR研究证明了不完全立方烷型和三金属立方烷型簇合物在溶液中的动态行为，这归因于簇核中的金属 - 金属键迁移以及与四方锥Re中心键合的二硫纶配体的假旋转，已发现这些过程进行的温度取决于簇核中所含金属中心的性质。
