CC Insertion over NCO of Allyl Isocyanate into the GeSi Bond of a Germylene
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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 CC bond into the GeSi 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 CC bond insertion between the GeSi 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.
