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Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
London Dispersion Interactions in Pnictogen Cations [ECl2 ]+ and [E=E]2+ (E=P, As, Sb) Supported by Anionic
Luong Phong Ho1, Alexandre Nasr1, Peter G Jones1
1Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.
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.
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