Bonding energy analysis in cationic borylene complexes of palladium and platinum: A theoretical study
作者： Krishna K. Pandey
DOI: 10.1016/J.POLY.2012.04.005
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摘要: Abstract Quantum chemical calculations at DFT/BP86/TZ2P have been carried out for cationic metal borylene complexes of palladium and platinum trans-[X(PMe3)2M(BR)]+ (X = Cl, Br, I; M = Pd, Pt; R = Mesityl, Xylyl, Ph, NMe2). The bonding analysis was with charge decomposition energy analysis. calculated geometry the complex trans-[Br(PMe3)2Pt(BMes)]+ is in excellent agreement experimental structural data trans-[Br(PCy3)2Pt(BMes)]+. Pauling bond order optimized structures shows that M–B bonds these multiple character, which also supported by performed orbital interactions between boron arise mainly from M ← BR σ donation. In all complexes, π contribution to relatively small. clearly [X(PMe3)2Pt(BR)]+ are more strongly stabilized Pt–BR than [X(PMe3)2Pd(BR)]+ probably reason [X(PCy3)2Pt(BMes)]+ could become isolated. contributions electrostatic interaction terms ΔEelstat M BR significantly larger covalent ΔEorb term. Thus, studied has a greater degree ionic character. gap HOMOs fragments [X(PMe3)2M)]+ LUMO BNMe2 allow weak [X(PMe3)2M]+ → BNMe2 π-back bonding.
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