Tallis Huw A, Newman Paul D, Edwards Peter G, Ooi Liling, Stasch Andreas
School of Chemistry, Cardiff University, Cardiff, UK.
Dalton Trans. 2008 Jan 7(1):47-53. doi: 10.1039/b715327a.
1-Trimethylsilylphosphirane, C2H4PSiMe3, has been prepared on a multi gram scale from P(SiMe3)3 via CICH2CH2P(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(eta5-C5H5)(eta6-C6H6) give rise tofac-M(CO)3(C2H4PSiMe3)3 and Fe(eta5-C5H5)(C2H4PSiMe3)3 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 andfac-Fe(eta5-C5H5)(C2H4PH)3 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.
1-三甲基硅基磷杂环丙烷(C₂H₄PSiMe₃)已通过CICH₂CH₂P(SiMe₃)₂由P(SiMe₃)₃以多克规模制备而成。C₂H₄PSiMe₃很容易发生质子解反应,以良好的产率生成热不稳定的母体磷杂环丙烷C₂H₄PH。C₂H₄PSiMe₃与fac-M(CO)₃(CH₃CN)₃(M = Cr、Mo)或Fe(η⁵-C₅H₅)(η⁶-C₆H₆)反应,分别生成fac-M(CO)₃(C₂H₄PSiMe₃)₃和Fe(η⁵-C₅H₅)(C₂H₄PSiMe₃)₃。游离的或配位的1-三甲基硅基磷杂环丙烷的质子解反应很容易导致P-Si键断裂,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。所有新配合物均通过分析和光谱方法进行了表征,并且还测定了fac-Cr(CO)₃(C₂H₄PSiMe₃)₃和fac-Mo(CO)₃(C₂H₄PH)₃的X射线晶体结构。