Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes

作者：Khoo Sabrina; Yeong Hui Xian; Li Yongxin; Ganguly Rakesh; So Cheuk Wai^*

来源：Inorganic Chemistry, 2015, 54(20): 9968-9975.

DOI：10.1021/acs.inorgchem.5b01759

The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:](2) (1, L = PhC(NtBu)(2)) with [Ir(cod)Cl](2) (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-mu-Cl-Ir(cod)}SiL] [(cod)IrCl2] (2). In contrast, the reaction of 1 with [Rh(cod)Cl](2) in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer-rhodium complex [LSi(Rh(cod)-mu-Cl-Rh(cod)}SiL] (3) and the dimeric amidinate-stabilized rhodosilylene [(LSi)mu-{Rh(mu-Cl)(2)Rh(cod)}](2) (4). Moreover, the latter reacted with PPh3 to afford a mixture of the Wilkinson's catalyst [(PPh3)(3)RhCl] and the dimeric rhodosilylene complex [(LSi)mu-{RhCl(PPh3)}](2) (5), which underwent a rearrangement to form the rhodosilylene-phosphidorhodium dimer (LSi)[mu-{RhCl(PPh3)}mu-{RhCl(LSiPh)}](PPh2) (6). Compounds 2-6 were characterized by NMR spectroscopy and X-ray crystallography. In addition, DFT calculations of compound 4 were performed to understand its electronic structure.

• 出版日期2015-10-19
• 单位南阳理工学院