923587-87-5Relevant academic research and scientific papers
Reactivity of the unsaturated hydride [Mo2(η5- C5H5)2(μ-H)(μ-PCy2)(CO) 2] toward 17- and 16-electron metal carbonyl fragments: Rational synthesis of electron-deficient heterometallic clusters
Alvarez, Celedonio M.,Alvarez, M. Angeles,Garcia, M. Esther,Ramos, Alberto,Ruiz, Miguel A.,Graiff, Claudia,Tiripicchio, Antonio
, p. 321 - 331 (2008/10/09)
Reactions of the 30-electron hydride [Mo2Cp2(μ-H) (μ-PCy2)(CO)2] (Cp = η5-C 5H5) with the 17-electron-fragment precursors [M 2Cp2(CO)n] (M = Mo, W, n = 6; M = Ru, n = 4) or [Mn2(CO)10] lead to the 46-electron clusters [Mo 2MCp3(μ-PCy2)(μ3-CO)(CO) 4] (M = Mo, W), [Mo2RuCp3(μ-PCy 2)(μ-CO)(CO)3], and [MnMo2Cp 2(μ-PCy2)(μ-CO)2(CO)5]. The structure of the trimolybdenum cluster was confirmed by an X-ray diffraction study and displays two long (ca. 3.1 A) and one short Mo-Mo distance (2.743(1) A). The title unsaturated hydride also proved to be highly reactive toward the appropriate precursors of 16-electron fragments such as M(CO) 5 (M = Cr, Mo, W) and MnCp′(CO)2 (Cp′ = η5-C5H4CH3), then leading to the 46-electron hydride clusters [MMo2Cp2(μ3-H) (μ-PCy2)(CO)7] (M = Cr, Mo, W) and [MnMo 2Cp2Cp′(μ3-H)(μ-PCy 2)(CO)4]. The structures of the compounds having Mo 2W and Mo2Mn skeletons were also determined by X-ray diffraction methods, both of them displaying Mo-Mo distances (ca. 2.6 A) somewhat shorter than expected for double Mo=Mo bonds and Mo - M distances longer than the corresponding single-bond lengths. A similar reaction takes place with the 12-electron compound CuCl, to give the hydride [CuMo 2ClCp2(μ3-H)(μ-PCy2)(CO) 2]. In contrast, the reaction of the title hydride with [Fe 2(CO)9], a precursor of the 16-electron fragment Fe(CO)4, gives the heterodinuclear complex [FeMo(μ-PCy 2)(CO)6] (Fe - Mo = 2.931(1) A).
