Synthesis and reactivity of N-heterocyclic carbene (NHC)-supported heavier nitrile ylides

The synthesis and isolation of stable heavier analogues of nitrile ylide as N-heterocyclic carbene (NHC) adducts of phosphasilenyl-tetrylene [(NHC)( Ter Ar)Si(H)PE 14 ( Ter Ar)] (E 14 = Ge 1 , Sn 2 ; Ter Ar = 2,6-Mes 2 C 6 H 3 , NHC = IMe 4 ) are reported. The delocalized Si-P-E 14 π-conjugation was examined experimentally and computationally. Interestingly, the germanium derivative 1 exhibits a 1,3-dipolar nature, leading to an unprecedented [3 + 2] cycloaddition with benzaldehyde, resulting in unique heterocycles containing four heteroatoms from group 14, 15, and 16. Further exploiting the nucleophilicity of germanium, activation of the P-P bond of P 4 was achieved, leading to a [(NHC)(phosphasilenyl germapolyphide)] complex. Moreover, the [3 + 2] cycloaddition and the σ-bond activation by 1 resemble the characteristics of the classic nitrile ylide. An NHC-stabilized heavier nitrile ylide activates white phosphorus, undergoing inorganic Huisgen-type [3 + 2] cycloaddition to form a unique heterocycle with four heteroatoms from groups 14, 15, and 16.