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1-三甲基硅基磷杂环丙烷作为一种配体以及作为磷杂环丙烷的稳定掩蔽试剂。

1-trimethylsilylphosphirane as a ligand and as a stable masked reagent for phosphirane.

作者信息

Tallis Huw A, Newman Paul D, Edwards Peter G, Ooi Liling, Stasch Andreas

机构信息

School of Chemistry, Cardiff University, Cardiff, UK.

出版信息

Dalton Trans. 2008 Jan 7(1):47-53. doi: 10.1039/b715327a.

Abstract

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.

摘要

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。

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