London Dispersion Interactions in Pnictogen Cations [ECl2]+ and [E=E]2+ (E=P, As, Sb) Supported by Anionic N‐Heterocyclic Carbenes

Abstract

Several pnictogen dihalide complexes of the type (WCA-IDipp)EX2 (E=P, As, Sb; X=Cl, Br) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA=B(C6 F5 )3 , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by salt metathesis reactions between the respective pnictogen trihalides EX3 and the lithium salt (WCA-IDipp)Li⋅toluene. Two-electron reduction of the dihalides (WCA-IDipp)EX2 with 1,3-bis(trimethylsilyl)-1,4-dihydropyrazine or elemental magnesium afforded the dipnictenes (WCA-IDipp)2 E2 , which display typical element-element double bonds as observed in diaryldiphosphenes, -arsenes and -stibenes. To provide an insight into the factors contributing to the structural stability of the pnictogen dihalide and dipnictene compounds, quantum chemical calculations were performed at the domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T)) level. A local energy decomposition (LED) analysis of the interaction between the carbene and the pnictogen dihalide or dipnictene moiety demonstrates that London dispersion is an essential factor for the stabilization of these compounds.