CC Insertion over NCO of Allyl Isocyanate into the GeSi Bond of a Germylene

Si Bond of a Germylene"/>

Two different isocyanates are reacted with PhC(NtBu)₂Ge–Si(SiMe₃)₃. While phenyl isocyanate undergoes catalytic cyclotrimerization, allyl isocyanate exhibits both cyclotrimerization and insertion of its CC bond into the GeSi bond. The differing reactivity behaviors are rationalized through detailed density functional theory calculations.

Two isocyanates are reacted with the germylene, PhC(NtBu)₂Ge-Si(SiMe₃)₃ (1). Phenyl isocyanate undergoes catalytic cyclotrimerization with 1 leading to 1,3,5-triphenyl isocyanurate (2), while allyl isocyanate undergoes both cyclotrimerization and the CC bond insertion between the GeSi bond. The constitution of 3 is determined by single-crystal X-ray studies. The contrasting reactivity pattern is explained by comprehensive density functional theory studies.

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