The reactivity of molybdenum pentachloride with ethers: routes to the synthesis of MoIVCl4 adducts, Mo(v) chlorido-alkoxides and Mo(v) oxydo-chlorides
作者:Fabio Marchetti、Guido Pampaloni、Stefano Zacchini
DOI:10.1039/c3dt51797g
日期:——
The reactivity of molybdenum pentachloride, 1, with a selection of mono- and diethers was investigated at room temperature in a non-coordinating solvent (dichloromethane). The Mo(IV) complex MoCl4(OMe2)2, 2, was obtained in 75% yield by the reaction of 1 with an excess of Me2O; similarly, MoCl4(κ2-L) [L = EtOCH2CH2OEt, 6a; MeOCH2CH(Me)OMe, 6b] were prepared in good yields by 1 : 1 combination of 1 with the appropriate diether. MoCl5 reacted with OMePh and Et2O affording variable amounts of RCl (R = Me and Et, respectively); MoCl3(OPh)2, 3, was isolated in 60% yield from 1 and OMePh. The reactions of 1 with OMetBu, OtBu(CHCH2), MeOCH2CH2OCH2Cl and 1,3-dioxane proceeded with non-selective activation of the organic material. The oxido-complexes Mo2O2Cl4(μ-OMe)2(μ-MeOH), 4, and MoOCl3(MeOH)2, 5, were isolated in modest amounts from 1/OMetBu, whereas MoOCl3(κ2-MeOCH2CH2OCH2Cl), 7, was obtained in 32% yield from 1/MeOCH2CH2OCH2Cl. All of the isolated metal products were characterized by spectroscopic and analytical techniques, and by X-ray diffractometry in the cases of 2, 4, 5, 6b and 7. NMR/GC-MS analyses were carried out in order to outline the fragmentation pathways of the organic reactants.
对钼五氯化物1与选定的单醚和二醚在无配位溶剂(二氯甲烷)中,室温下进行了反应性研究。通过1与过量的Me2O反应,获得了75%产率的Mo(IV)配合物MoCl4(OMe2)2,2;同样,MoCl4(κ2-L) [L = EtOCH2CH2OEt, 6a;MeOCH2CH(Me)OMe, 6b] 通过1与适当的二醚以1:1的组合反应获得,产率良好。MoCl5与OMePh和Et2O反应,产生了可变量的RCl(R = Me和Et);从1与OMePh的反应中分离得到了60%产率的MoCl3(OPh)2,3。1与OMetBu、OtBu(CHCH2)、MeOCH2CH2OCH2Cl和1,3-二恶烷的反应则以非选择性方式激活了有机物质。氧化物络合物Mo2O2Cl4(μ-OMe)2(μ-MeOH),4和MoOCl3(MeOH)2,5分别从1/OMetBu中以适量分离得到,而MoOCl3(κ2-MeOCH2CH2OCH2Cl),7则从1/MeOCH2CH2OCH2Cl中获得,产率为32%。所有分离的金属产物都通过光谱和分析技术进行了表征,在2、4、5、6b和7的情况下则使用了X射线衍射法。还进行了NMR/GC-MS分析,以概述有机反应物的裂解路径。