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Hydrosilylation of a Silicon(II) Hydride: Synthesis and Characterization of a Remarkable Silylsilylene

  作者 ZHANG SHUHUA; YEONG HUIXIAN; XI HONGWEI; LIM KOK HWA; SO CHEUKWAI  
  选自 期刊  Chemistry-A European Journal;  卷期  2010年16-33;  页码  10250-10254  
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[摘要]The synthesis and characterization of novel monomeric silylsilyl [{PhC(NtBu)(2)}Si-Si{(NtBu)(2)(H)Ph}R] (R= Cl (2), H (4)) are described. Compound 2 was prepared by the treatment of [{PhC(NtBu)(2)}SiHCl2] (1) with two equivalents of potassium graphite, whereas compound 4 was synthesized by the treatment of 1 with four equivalents of potassium graphite. The results suggest that silicon(II) hydride intermediate [{PhC(NtBu)(2)}SiH] was formed in the reduction, which underwent a hydrosilylation with the amidinate ligand of [{PhC(NtBu)(2)}SiR] (R= Cl or H) to form 2 and 4, respectively. The existence of [{PhC(NtBu)(2)}SiH] in solution was demonstrated by the treatment of [{PhC( NtBu)(2)}SiCl] (3) with [K{HB(iBu)(3)}]. Compounds 2 and 4 have been characterized by X-ray crystallography and NMR spectroscopy. The results show that compounds 2 and 4 are stable in solution or the solid state, and do not dimerize to form the corresponding disilene. DFT calculations show that the Si-Si bonds in 2 and 4 do not have multiple-bond character.

 
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