Selective Si-C(sp³) bond cleavage of a silyl-bridged amido alkyl ligand in an yttrium complex

Compared with Si-C(sp² and sp) bonds bearing neighboring π-bond hyperconjugative interactions, the activation of robust Si-C(sp³) bonds has proved to be a challenge. Herein, two distinct Si-C(sp³) bond cleavages have been realized by rare-earth-mediated and nucleophilic addition of unsaturated substrates. The reactions of Tp^Me2Y[κ²-(C,N)-CH(SiH₂Ph)SiMe₂NSiMe₃](THF) (1) with CO or CS₂ gave two endocyclic Si-C bond cleavage products, Tp^Me2Y[κ²-(O,N)-OCCH(SiH₂Ph)SiMe₂NSiMe₃](THF) (2) and Tp^Me2Y[κ²-(S,N)-SSiMe₂NSiMe₃](THF) (3), respectively. However, 1 reacted with nitriles such as PhCN and p-R'C₆H₄CH₂CN in a 1 : 1 molar ratio to yield the exocyclic Si-C bond products Tp^Me2Y[κ²-(N,N)-N(SiH₂Ph)C(R)CHSiMe₂NSiMe₃](THF) (R = Ph (4); R = C₆H₅CH₂ (6H); R = p-F-C₆H₄CH₂ (6F); and R = p-MeO-C₆H₄CH₂ (6MeO)), respectively. Moreover, complex 4 can continuously react with an excess of PhCN to form a Tp^Me2-supported yttrium complex with a novel pendant silylamido-substituted β-diketiminato ligand, Tp^Me2Y[κ³-(N,N,N)-N(SiH₂Ph)C(Ph)CHC(Ph)N-SiMe₂NSiMe₃](PhCN) (5).