화학공학소재연구정보센터
Inorganic Chemistry, Vol.57, No.10, 5879-5887, 2018
B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand
The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me3Si)N}SiBH3] [1; L = PhC(NtBu)(2), and Ar = 2,6-iPr(2)C(6)H(3)] with MeOTf in toluene at room temperature formed [L{Ar(Me3SON}SiBH2OTf] (2). [LSiN(SiMe3)Ar] in compound 2 then underwent a B-H bond activation with BH2OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe3)Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(mu-kappa 1:kappa 1-L)B(H)(DMAP)Si(H){N(Ar)SiMe3}]OTf (4) was afforded. Mechanistic studies show that "(mu-kappa 1:kappa 1-L)B(H)(OTf)Si(H){N(Ar)SiMe3)" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl2 by the amidinato silicon(I) dimer [LSi:](2) to form the B-Cl bond activation product [(mu-kappa 1:kappa 1-L)B(Cl)(Ph)Si(Cl)](2) (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.