Terpene dispersion energy donor ligands in borane complexes
Terpene dispersion energy donor ligands in borane complexes
复制标题
硼烷配合物中萜烯分散能量供体配体
DOI：
10.1039/d2cc04203g
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发表时间：
2022
影响因子：
4.9
通讯作者：
Power, Philip P.
中科院分区：
文献类型：
--
作者：
Mears, Kristian L.;Kutzleb, Michelle A.;Stennett, Cary R.;Fettinger, James C.;Kaseman, Derrick C.;Yu, Ping;Vasko, Petra;Power, Philip P.
配合物[B（β-蒎烷）3]（1）的结构表征显示了非共价H-H接触，这与涉及β-蒎烷配体框架的伦敦分散能的产生一致。计算研究了化合物1、[B（顺式）3]（2）和[B（顺式）3]（3）的均裂断裂。等键交换结果表明，伦敦分散相互作用高度依赖于萜烯的立体化学，β-蒎烷骨架提供了最大的分散自由能（ΔG = −7.9 kcal mol−1），采用了格里姆的分散校正（D3 BJ）。PMe 3与[B（β-pinane）3]配位，得到配合物[Me 3 P-B（β-pinane）3]（4），该配合物在溶液中表现出动态配位平衡。缔合过程在302 K时有轻微的吸能作用（ΔG = +0.29 kcal mol−1）。
Structural characterization of the complex [B(β-pinane)3] (1) reveals non-covalent H⋯H contacts that are consistent with the generation of London dispersion energies involving the β-pinane ligand frameworks. The homolytic fragmentations of 1, and camphane and sabinane analogues ([B(camphane)3] (2) and [B(sabinane)3] (3)) were studied computationally. Isodesmic exchange results showed that London dispersion interactions are highly dependent on the terpene's stereochemistry, with the β-pinane framework providing the greatest dispersion free energy (ΔG = −7.9 kcal mol−1) with Grimme's dispersion correction (D3BJ) employed. PMe3 was used to coordinate to [B(β-pinane)3], giving the complex [Me3P–B(β-pinane)3] (4), which displayed a dynamic coordination equilibrium in solution. The association process was found to be slightly endergonic at 302 K (ΔG = +0.29 kcal mol−1).