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

作者：Zhang Shu Hua; Yeong Hui Xian; Xi Hong Wei; Lim Kok Hwa; So Cheuk Wai^*

来源：Chemistry - A European Journal, 2010, 16(33): 10250-10254.

DOI：10.1002/chem.201000089

• carbene homologues
• N ligands
• silicon
• silylenes

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)}SiHCl(2)] (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.

• 出版日期2010-9-3
• 单位南阳理工学院