Herbst K, Monari M, Brorson M
Haldor Topsøe A/S, Nymøllevej 55, DK-2800 Lyngby, Denmark.
Inorg Chem. 2001 Jun 18;40(13):2979-85. doi: 10.1021/ic001129c.
Reaction of the methylcyclopentadienyl (Cp') cluster compound [(eta(5)-Cp')(3)Mo(3)S(4)][pts] (pts = p-toluenesulfonate) with noble metal alkene complexes resulted in the formation of four new heterobimetallic cubane-like Mo(3)S(4)M' cluster cores (M' = Ru, Os, Rh, Ir). Thus, reaction with [(1,5-cod)Ru(CO)(3)] or [(1,3-cod)Os(CO)(3)] (cod = cyclooctadiene) afforded [(eta(5)-Cp')(3)Mo(3)S(4)M'(CO)(2)][pts] (M' = Ru: [1][pts]; M' = Os: [2][pts]). When [1][pts] was kept in CH(2)Cl(2)/pentane solution, partial loss of carbonyl ligands occurred and the carbonyl-bridged dicubane cluster [((eta(5)-Cp')(3)Mo(3)S(4)Ru)(2)(mu-CO)(3)]pts was isolated. An X-ray crystal structure revealed the presence of the hitherto unobserved Ru(mu-CO)(3)Ru structural element. The formation of cluster compounds containing Mo(3)S(4)Rh and Mo(3)S(4)Ir cores was achieved in boiling methanol by reacting [(eta(5)-Cp')(3)Mo(3)S(4)][pts] with M'Cl(cyclooctene)(2) (M' = Rh, Ir) in the presence of PPh(3). In this way [(eta(5)-Cp')(3)Mo(3)S(4)M'Cl(PPh(3))][pts] (M' = Rh, Ir) could be isolated. An alternative route to the Mo(3)S(4)Rh cluster core was found in the reaction of [(eta(5)-Cp')(3)Mo(3)S(4)][pts] with RhCl(1,5-cod), which yielded [(eta(5)-Cp')(3)Mo(3)S(4)Rh(cod)]pts ([7]pts). Substitution of the cod ligand in [7]pts by 1,3-bis(diphenylphosphanyl)propane (dppp) gave [(eta(5)-Cp')(3)Mo(3)S(4)Rh(dppp)]pts.
甲基环戊二烯基（Cp'）簇合物[(η⁵-Cp')₃Mo₃S₄][pts]（pts = 对甲苯磺酸盐）与贵金属烯烃配合物反应生成了四个新的异双金属类立方烷型Mo₃S₄M'簇核（M' = Ru、Os、Rh、Ir）。因此，与[(1,5-环辛二烯)Ru(CO)₃]或[(1,3-环辛二烯)Os(CO)₃]（环辛二烯 = cod）反应得到[(η⁵-Cp')₃Mo₃S₄M'(CO)₂][pts]（M' = Ru：[1][pts]；M' = Os：[2][pts]）。当[1][pts]保存在二氯甲烷/戊烷溶液中时，羰基配体部分损失，分离得到了羰基桥连的双立方烷簇合物[((η⁵-Cp')₃Mo₃S₄Ru)₂(μ-CO)₃][pts]₂。X射线晶体结构揭示了迄今未观察到的Ru(μ-CO)₃Ru结构单元的存在。在沸腾的甲醇中，通过[(η⁵-Cp')₃Mo₃S₄][pts]与[M'Cl(环辛烯)₂]₂（M' = Rh、Ir）在三苯基膦存在下反应，实现了含Mo₃S₄Rh和Mo₃S₄Ir簇核的簇合物的形成。通过这种方式可以分离得到[(η⁵-Cp')₃Mo₃S₄M'Cl(PPh₃)][pts]（M' = Rh、Ir）。在[(η⁵-Cp')₃Mo₃S₄][pts]与[RhCl(1,5-环辛二烯)]₂的反应中发现了一条通往Mo₃S₄Rh簇核的替代路线，该反应生成[(η⁵-Cp')₃Mo₃S₄Rh(环辛二烯)][pts]₂（[7][pts]₂）。用1,3-双（二苯基膦基）丙烷（dppp）取代[7][pts]₂中的环辛二烯配体，得到[(η⁵-Cp')₃Mo₃S₄Rh(dppp)][pts]₂。
