Belletti Daniele, Graiff Claudia, Massera Chiara, Minarelli Alex, Predieri Giovanni, Tiripicchio Antonio, Acquotti Domenico
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, Parco Area delle Scienze 17/A, 43100 Parma, Italy.
Inorg Chem. 2003 Dec 15;42(25):8509-18. doi: 10.1021/ic034887m.
The reactions of [M3(CO)12] (M=Ru or Fe) with 1,2 bis[(diphenylphosphino)methyl]benzene diselenide (dpmbSe2) in hot toluene afford a variety of phosphine-substituted selenido carbonyl clusters. They belong to the following three families: (i) 50-electron clusters with a M3Se2 core (2, 3, 5-7), (ii) 48-electron clusters with a M3Se core (1, 8), (iii) 34-electron clusters with a M2Se2 core (4). All these species derive from the P=Se bond cleavage. Cluster 1, which contains a hydrido, a phosphido, and a carbene ligand, is produced by multiple fragmentation of the diphosphine. This fragmentation appears related to the presence of the selenido ligand on the cluster, as the reaction of [Ru3(CO)12] with dpmb (not selenized) produces only carbonyl substitution by the phosphine to give [Ru3(CO)10(mu-dpmb)] (9). All the clusters synthesized have been characterized by spectroscopic techniques, and in some cases fluxional behavior has been detected in solution by NMR analysis. The structures of 1, 2, and 7-9 have been determined by X-ray diffraction methods.
[M₃(CO)₁₂]（M = Ru 或 Fe）与 1,2 - 双[(二苯基膦基)甲基]苯二硒化物（dpmbSe₂）在热甲苯中反应，生成了多种膦取代的硒羰基簇合物。它们属于以下三个家族：（i）具有 M₃Se₂ 核心的 50 电子簇合物（2、3、5 - 7），（ii）具有 M₃Se 核心的 48 电子簇合物（1、8），（iii）具有 M₂Se₂ 核心的 34 电子簇合物（4）。所有这些物种都源自 P = Se 键的断裂。簇合物 1 包含一个氢化物、一个磷化物和一个卡宾配体，它是由二膦的多重碎片化产生的。这种碎片化似乎与簇合物上硒配体的存在有关，因为[Ru₃(CO)₁₂]与 dpmb（未硒化）的反应仅产生膦对羰基的取代，生成[Ru₃(CO)₁₀(μ - dpmb)]（9）。所有合成的簇合物都通过光谱技术进行了表征，并且在某些情况下，通过 NMR 分析在溶液中检测到了分子内重排行为。1、2 和 7 - 9 的结构已通过 X 射线衍射方法确定。
