Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh_2 and MoIr_2 mixed-metal sulfido clusters
Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh_2 and MoIr_2 mixed-metal sulfido clusters
复制标题
含四膦共配体的Mo双氢硫配合物的制备及其转化为MoRh_2和MoIr_2混合金属硫簇簇
DOI：
10.1039/b902386k
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发表时间：
2009
影响因子：
4
通讯作者：
Yasushi Mizobe
中科院分区：
文献类型：
--
作者：
Kentaro Iwasa;Hidetake Seino;Fumiya Niikura;Yasushi Mizobe
Mo(0)配合物与四膦共配体[Mo(κ4-P4)(Ph2PCH2CH2PPh2)] （P4 = meso-o-C6H4(PPhCH2CH2PPh2)2）在室温下用H2S气体在甲苯中处理得到[Mo(SH)2(κ4-P4)](1)，得到了第一个Mo(II) - bis（hydrosulfido）配合物。它的三角棱柱结构很少观察到Mo（II）配合物已确定的x射线分析。在NEt3的存在下，1与[RhCl(CO)2]2和[IrCl(CO)2（对甲苯胺）]反应形成了硫桥接的三核簇[Mo(κ4-P4)(μ3-S)2{Rh(CO)2}2](4)和[Mo(κ4-P4)(μ3-S)2{Ir(CO)2}2](5)。x射线衍射研究表明，固态的MoRh2簇4以两种异构体形式存在，这是由P4与三角棱柱Mo中心的不同取向引起的，而Ir类似物5的晶体只包含与4观察到的两种异构体中的一种相对应的分子。1、4和5在溶液中的通量特征已被VT核磁共振研究证实。
The treatment of a Mo(0) complex with a tetraphosphine co-ligand [Mo(κ4-P4)(Ph2PCH2CH2PPh2)] (P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with H2S gas in toluene at room temperature afforded [Mo(SH)2(κ4-P4)] (1), which demonstrates the first Mo(II) bis(hydrosulfido) complex. Its trigonal-prismatic structure rarely observed for Mo(II) complexes has been determined by X-ray analysis. The reactions of 1 with [RhCl(CO)2]2 and [IrCl(CO)2(p-toluidine)] in the presence of NEt3 resulted in the formation of the sulfido-bridged trinuclear clusters [Mo(κ4-P4)(μ3-S)2{Rh(CO)2}2] (4) and [Mo(κ4-P4)(μ3-S)2{Ir(CO)2}2] (5), respectively. The X-ray diffraction study has disclosed that the MoRh2 cluster 4 in the solid state exists in two isomeric forms arising from the different orientation of P4 to the trigonal-prismatic Mo center, whereas the crystals of the Ir analogue 5 contains the molecules corresponding to only one of the two isomers observed for 4. The fluxional features of 1, 4, and 5 in solution have been confirmed by VT NMR studies.