η^6-[三(三甲基硅基)苯基硅烷]三羰基钼化合物的合成、结构及硅-硅键的稳定性

Synthesis,Structure and Si—Si Bond Stability of η^6-[Tris（trimethylsilyl）phenylsilane]tricarbonylmolybdenum Complexes

在三氟化硼存在下,三(三甲基硅基)苯基硅烷(Me3Si)3SiC6H4R(R=H,p-Me和p-MeO)与三吡啶三羰基钼反应得到相应的η6-[三(三甲基硅基)苯基硅烷]三羰基钼类化合物η6-[(Me3Si)3SiC6H4R].Mo(CO)3.利用1H NMR,13C NMR,IR和元素分析对3个化合物进行了鉴定,并利用单晶X射线衍射法测定了化合物η6-[(Me3Si)3SiC6H4R]Mo(CO)3(R=H)的分子结构.考察了这些化合物中硅-硅键被过渡金属活化的可能,结果表明,在加热条件下这些化合物中硅-硅键不与分子内过渡金属发生相互作用.

Intramolecular activation of Si—Si bond by transition metals had been found to occur in many types of complexes,including those containing polysilanyl groups linked to η4-and η5-ligands.However,whether such Si—Si bond activation could occur in η6-phenyl complexes remains unclear.In this study,η6-[tris（trimethylsilyl）phenylsilane]tricarbonylmolybdenum（R=H,p-Me and p-MeO） were synthesized through reactions of tris（trimethylsilyl）phenylsilane（SiMe3）3SiC6H4R with tripyridine（tricarbonyl）molybdenum in the presence of boron trifluoride.The complexes obtained were characterized by 1H NMR,13C NMR,IR spectra and elemental analysis.The molecular structure of η6-[（SiMe3）3SiC6H4R]Mo（CO）3（R=H） was determined by the X-ray diffraction method.The possibility of the Si—Si bond activation by the intramolecular transition metal was studied.The results show that the Si—Si bonds in the complexes are stable under thermal conditions and hence unable to interact with the intramolecular transition metal.