London Dispersion Effects in a Distannene/Tristannane Equilibrium: Energies of their Interconversion and the Suppression of the Monomeric Stannylene Intermediate
London Dispersion Effects in a Distannene/Tristannane Equilibrium: Energies of their Interconversion and the Suppression of the Monomeric Stannylene Intermediate
复制标题
远锡烯/三锡烷平衡中的伦敦色散效应：它们相互转化的能量和单体锡烯中间体的抑制
DOI：
10.1002/anie.202301919
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Power, Philip P.
中科院分区：
文献类型：
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作者：
Zou, Wenxing;Bursch, Markus;Mears, Kristian L.;Stennett, Cary R.;Yu, Ping;Fettinger, James C.;Grimme, Stefan;Power, Philip P.
新的色散能供体配体2，4，6-三环戊基苯基的{LiC6H2−2，4，6-⋅Et2O}2(Cyp=环戊基)(1)与SnCl2反应，得到茂烯{Sn(C6H2−2，4，6-CyP3)2}2(2)和环三锡烷{Sn(C6H2−2，4，4，6-Cyp3)2}3(3).2在较高温度(345 K或以上)的溶液中较好，而3在298 K附近较好。Van‘t Hoff分析表明，3到2的转化为ΔH=33.36 kcal −1和ΔS=0.102 kcal −1K−1，得到ΔG300K=+2.86 kcal mol−1，表明3到2的转化是一个带电过程。计算结果表明，DED在3中的稳定度为−28.5kcal −1/{Sn(C6H2−2，4，6-Cyp3)2单位，这超过了−2中的DED能量16.3kcal −1/单位。数据清楚地表明，色散相互作用是3to2平衡的主要仲裁者。2和3都具有较大的分散稳定能，可以抑制单体解离(EDA结果支持)。
Reaction of {LiC6H2−2,4,6‐Cyp3⋅Et2O}2(Cyp=cyclopentyl) (1) of the new dispersion energy donor (DED) ligand, 2,4,6‐triscyclopentylphenyl with SnCl2afforded a mixture of the distannene {Sn(C6H2−2,4,6‐Cyp3)2}2(2), and the cyclotristannane {Sn(C6H2−2,4,6‐Cyp3)2}3(3).2is favored in solution at higher temperature (345 K or above) whereas3is preferred near 298 K. Van't Hoff analysis revealed the3to2conversion has a ΔH=33.36 kcal mol−1and ΔS=0.102 kcal mol−1K−1, which gives a ΔG300 K=+2.86 kcal mol−1, showing that the conversion of3to2is an endergonic process. Computational studies show that DED stabilization in3is −28.5 kcal mol−1per {Sn(C6H2−2,4,6‐Cyp3)2unit, which exceeds the DED energy in2of −16.3 kcal mol−1per unit. The data clearly show that dispersion interactions are the main arbiter of the3to2equilibrium. Both2and3possess large dispersion stabilization energies which suppress monomer dissociation (supported by EDA results).