Departamento de Química Inorgánica, Instituto Universitario de Catálisis Homogénea, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-C.S.I.C. 50009 Zaragoza, Spain.
Chemistry. 2011 Jul 11;17(29):8115-28. doi: 10.1002/chem.201100138. Epub 2011 Jun 1.
The treatment of [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{M(μ-Cl)(diolef)}(2)] (diolef=diolefin) in the presence of NEt(3) affords the hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene (tfb) for 3) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] with [{Rh(μ-OMe)(cod)}(2)], although the main product of the reaction with [{Ir(μ-OMe)(cod)}(2)] was [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh(3))}(2)] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2) (diolef)(PPh(3))(2)] (diolef=cod for 6, nbd for 7) and [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh(3) ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.
用 NEt(3)处理 [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] 与 [{M(μ-Cl)(diolef)}(2)]（diolef=二烯烃），得到氢化物-硫化物簇 [Rh(3)(μ-H)(μ(3)-S)(2)(diolef){P(OPh)(3)}(4)]（diolef=1,5-环辛二烯（cod）为 1，2,5-降冰片二烯（nbd）为 2，四氟苯并[5,6]双环[2.2.2]辛-2,5,7-三烯（tfb）为 3）和 [Rh(2)Ir(μ-H)(μ(3)-S)(2)(cod){P(OPh)(3)}(4)]（4）。尽管 [{Rh(μ-OMe)(cod)}(2)] 与 [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] 反应的主要产物是 [RhIr(2)(μ-H)(μ(3)-S)(2)(cod)(2){P(OPh)(3)}(2)]（5），但 1 也可以通过用 [{Rh(μ-SH){P(OPh)(3)}(2)}(2)] 处理 [{Rh(μ-OMe)(cod)}(2)] 来获得。通过 [M(acac)(diolef)]（acac=乙酰丙酮化物）对 [{Rh(μ-SH)(CO)(PPh(3))}(2)] 中氢硫化物配体的去质子化，生成氢化物-硫化物簇 [Rh(3)(μ-H)(μ(3)-S)(2)(CO)(2)（diolef）(PPh(3))(2)]（diolef=cod 为 6，nbd 为 7）和 [Rh(2)Ir(μ-H)(μ(3)-S)(2)(CO)(2)(cod)(PPh(3))(2)]（8）。在溶液中，1-3 和 5 以两种相互转化的异构体形式存在，其中桥接氢化物配体位于不同的边缘。8 存在三种异构体，这是由簇中 PPh(3)配体的位置（顺式和反式）和氢化物配体的位置决定的。具有大体积三苯基膦酸酯配体的簇的动态行为涉及氢从铑向硫的迁移，同时氢化物的特征向质子特征转变，这对于理解金属硫化物加氢处理催化剂表面上的氢扩散具有重要意义。
