A (U)MP2(full) and (U)CCSD(T) theoretical investigation into the substituent effects on the cation-it interactions between M+ (M = Li or Na) and LBBL (L = -H, -CH3, -OH, -CN, -NC, -F, :CO, :NN, :BH, :CN-, :NC- and :OH-)

作者：Yang, Zhao-ming; Zhang, Lin; Chen, Li-zhen; Ren, Fu-de^*; Du, Shan; Wang, Yong

来源：Computational and Theoretical Chemistry, 2011, 978(1-3): 110-122.

DOI：10.1016/j.comptc.2011.09.044

• BB multiple bond
• Substituent effect
• Cation-pi interaction
• "Truncated" model

The substituent effects on the cation-re interactions are investigated between M+ (M = Li or Na) and LBBL (L = -H, -CH3, -OH, -CN, -NC, -F, :CO, :NN, :BH, :CN-, :NC- and :OH-) using (U)MP2(full) and (U)CCSD(T) methods at 6-311+G(2d) (or 6-311++G(2d,p)) and aug-cc-pVTZ levels. The B B triple-bond contraction is found in the complex with the lone-pair-electron donors in comparison with the monomer. The binding energies follow the order of (HOB BOH)(2-) center dot center dot center dot M+ > (CNB BNC)(2-) center dot center dot center dot M+, HOB=BOH center dot center dot center dot M+ > H3CB=BCH3 center dot center dot center dot M+ > HBB BBH center dot center dot center dot M+ > HB=BH center dot center dot center dot M+ > (CNB BNC)(2-)center dot center dot center dot M+ > CNB=BNC center dot center dot center dot M+ > NCB=BCN center dot center dot center dot M+. The electron-donating substituent increases electron density of the BB multiple bond by means of the p-pi, pi-pi conjugative or sigma-pi hyperconjugative effects upon complexation, resulting in the increased cation-re interaction compared with that of the unsubstituted HBBH center dot center dot center dot M+, while the electron-withdrawing substituent decreases the cation-re interaction. The analyses of the APT atomic charge, "truncated" model, natural bond orbital (NBO), atoms in molecules (AIM) and electron density shifts reveal the nature of the substituent effects and explain the origin of the B B bond contraction.

• 出版日期2011-12-30
• 单位中北大学