1-Trimethylsilylphosphirane as a ligand and as a stable masked reagent for phosphirane
作者:Huw A. Tallis、Paul D. Newman、Peter G. Edwards、Liling Ooi、Andreas Stasch
DOI:10.1039/b715327a
日期:——
1-Trimethylsilylphosphirane, C2H4PSiMe3, has been prepared on a multi gram scale from P(SiMe3)3via ClCH2CH2P(SiMe3)2. C2H4PSiMe3 is readily susceptible to protonolysis forming the thermally unstable parent phosphirane, C2H4PH, in good yields. Reaction of C2H4PSiMe3 with fac-M (CO)3(CH3CN)3 (M = Cr, Mo) or [Fe(η5-C5H5)(η6-C6H6)](PF6) give rise to fac-M(CO)3(C2H4PSiMe3)3 and [Fe(η5-C5H5)(C2H4PSiMe3)3](PF6) respectively. Protonolysis of the free or coordinated 1-trimethylsilylphosphirane readily causes P–Si cleavage to give rise to the parent C2H4PH or the respective complexes, fac-M(CO)3(C2H4PH)3 and fac-[Fe(η5-C5H5)(C2H4PH)3](PF6) in situ. All new complexes are characterised by analytical and spectroscopic methods and the X-ray crystal structures of fac-Cr(CO)3(C2H4PSiMe3)3 and fac-Mo(CO)3(C2H4PH)3 have also been determined.
通过 ClCH2CH2P(SiMe3)2 从 P(SiMe3)3制备出了多克级的 1-三甲基硅基膦环烷 C2H4PSiMe3。C2H4PSiMe3 很容易被质子分解,形成热不稳定的母体膦烷 C2H4PH,产量很高。C2H4PSiMe3 与 fac-M (CO)3(CH3CN)3 (M = Cr、Mo)或 [Fe(η5-C5H5)(η6-C6H6)](PF6)反应,分别生成 fac-M(CO)3(C2H4PSiMe3)3 和 [Fe(η5-C5H5)(C2H4PSiMe3)3](PF6)。游离的或配位的 1-三甲基硅基膦环容易导致 P-Si 裂解,从而在原位生成母体 C2H4PH 或相应的配合物 fac-M(CO)3(C2H4PH)3 和 fac-[Fe(η5-C5H5)(C2H4PH)3](PF6)。所有新复合物都通过分析和光谱方法进行了表征,并确定了 fac-Cr(CO)3(C2H4PSiMe3)3和 fac-Mo(CO)3(C2H4PH)3的 X 射线晶体结构。