Reactivity of the Unsaturated Hydride [Mo2(5-C5H5)2(
详细信息 查看全文
- 作者：Celedonio M. Alvarez ; M. Angeles Alvarez ; M. Esther Garcí ; a ; Alberto Ramos ; Miguel A. Ruiz ; Claudia Graiff ; Antonio Tiripicchio
- 刊名：Organometallics
- 出版年：2007
- 出版时间：January 15, 2007
- 年：2007
- 卷：26
- 期：2
- 页码：321 - 331
- 全文大小：189K
- 年卷期：v.26,no.2(January 15, 2007)
- ISSN：1520-6041
文摘
Reactions of the 30-electron hydride [Mo2Cp2(
-H)(-PCy2)(CO)2] (Cp = 
5-C5H5) with the 17-electron-fragment precursors [M2Cp2(CO)n] (M = Mo, W, n = 6; M = Ru, n = 4) or [Mn2(CO)10] lead to the46-electron clusters [Mo2MCp3(-PCy2)(3-CO)(CO)4] (M = Mo, W), [Mo2RuCp3(-PCy2)(-CO)(CO)3],and [MnMo2Cp2(-PCy2)(-CO)2(CO)5]. The structure of the trimolybdenum cluster was confirmed byan X-ray diffraction study and displays two long (ca. 3.1 Å) and one short Mo-Mo distance (2.743(1)Å). The title unsaturated hydride also proved to be highly reactive toward the appropriate precursors of16-electron fragments such as M(CO)5 (M = Cr, Mo, W) and MnCp'(CO)2 (Cp' = 5-C5H4CH3), thenleading to the 46-electron hydride clusters [MMo2Cp2(3-H)(-PCy2)(CO)7] (M = Cr, Mo, W) and[MnMo2Cp2Cp'(3-H)(-PCy2)(CO)4]. The structures of the compounds having Mo2W and Mo2Mnskeletons were also determined by X-ray diffraction methods, both of them displaying Mo-Mo distances(ca. 2.6 Å) somewhat shorter than expected for double Mo=Mo bonds and Mo-M distances longer thanthe corresponding single-bond lengths. A similar reaction takes place with the 12-electron compoundCuCl, to give the hydride [CuMo2ClCp2(3-H)(-PCy2)(CO)2]. In contrast, the reaction of the title hydridewith [Fe2(CO)9], a precursor of the 16-electron fragment Fe(CO)4, gives the heterodinuclear complex[FeMo(-PCy2)(CO)6] (Fe-Mo = 2.931(1) Å).
-H)(-PCy2)(CO)2] (Cp = 5-C5H5) with the 17-electron-fragment precursors [M2Cp2(CO)n] (M = Mo, W, n = 6; M = Ru, n = 4) or [Mn2(CO)10] lead to the46-electron clusters [Mo2MCp3(-PCy2)(3-CO)(CO)4] (M = Mo, W), [Mo2RuCp3(-PCy2)(-CO)(CO)3],and [MnMo2Cp2(-PCy2)(-CO)2(CO)5]. The structure of the trimolybdenum cluster was confirmed byan X-ray diffraction study and displays two long (ca. 3.1 Å) and one short Mo-Mo distance (2.743(1)Å). The title unsaturated hydride also proved to be highly reactive toward the appropriate precursors of16-electron fragments such as M(CO)5 (M = Cr, Mo, W) and MnCp'(CO)2 (Cp' = 5-C5H4CH3), thenleading to the 46-electron hydride clusters [MMo2Cp2(3-H)(-PCy2)(CO)7] (M = Cr, Mo, W) and[MnMo2Cp2Cp'(3-H)(-PCy2)(CO)4]. The structures of the compounds having Mo2W and Mo2Mnskeletons were also determined by X-ray diffraction methods, both of them displaying Mo-Mo distances(ca. 2.6 Å) somewhat shorter than expected for double Mo=Mo bonds and Mo-M distances longer thanthe corresponding single-bond lengths. A similar reaction takes place with the 12-electron compoundCuCl, to give the hydride [CuMo2ClCp2(3-H)(-PCy2)(CO)2]. In contrast, the reaction of the title hydridewith [Fe2(CO)9], a precursor of the 16-electron fragment Fe(CO)4, gives the heterodinuclear complex[FeMo(-PCy2)(CO)6] (Fe-Mo = 2.931(1) Å).