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Quantum Chemical Investigation of Dimerization in the Schlenk Equilibrium of Thiophene Grignard Reagents.
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-02-18 , DOI: 10.1021/acs.jpca.9b09985 Ethan R Curtis 1 , Matthew D Hannigan 1 , Andrew K Vitek 1 , Paul M Zimmerman 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-02-18 , DOI: 10.1021/acs.jpca.9b09985 Ethan R Curtis 1 , Matthew D Hannigan 1 , Andrew K Vitek 1 , Paul M Zimmerman 1
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The Schlenk equilibrium of Grignard reagents describes the intricate relationships between monomers, aggregates, and exchange products. The core step of the Schlenk equilibrium, formally 2RMgX ⇌ R2Mg + MgX2, has been subject to computational studies of simple methyl Grignards and NMR determination of thermodynamics. These studies neglect the effect the R group may have on the accessibility of intermediates in the Schlenk equilibrium. In this study, computational reaction discovery tools were employed to thoroughly search the chemical space for feasible dimerizations and pathways to ligand exchange for thiophene Grignards. Three bridged dimers, μ-(Cl, C), μ-(Cl, Cl), and μ-Cl, were found to be vital intermediates, which are stabilized by π-interactions involving the thiophene group. These dimers are approximately as thermodynamically stable as the Grignard monomers and its ligand exchange products, and therefore, their reactivity should be considered when examining mechanisms for aryl Grignard or cross-coupling reactions.
中文翻译：
噻吩格利雅试剂Schlenk平衡中二聚化的量子化学研究。
格氏试剂的Schlenk平衡描述了单体，聚集体和交换产物之间的复杂关系。Schlenk平衡的核心步骤正式为2RMgX R2Mg + MgX2，已通过简单甲基格氏试剂的计算研究和热力学的NMR测定进行了研究。这些研究忽略了R基团对Schlenk平衡中中间体可及性的影响。在这项研究中，使用了计算反应发现工具来彻底搜索化学空间中可行的二聚化和噻吩格氏试剂配体交换的途径。发现三个桥接的二聚体，μ-（Cl，C），μ-（Cl，Cl）和μ-Cl是重要的中间体，它们通过涉及噻吩基团的π相互作用而稳定。
更新日期：2020-02-18
中文翻译：
噻吩格利雅试剂Schlenk平衡中二聚化的量子化学研究。
格氏试剂的Schlenk平衡描述了单体，聚集体和交换产物之间的复杂关系。Schlenk平衡的核心步骤正式为2RMgX R2Mg + MgX2，已通过简单甲基格氏试剂的计算研究和热力学的NMR测定进行了研究。这些研究忽略了R基团对Schlenk平衡中中间体可及性的影响。在这项研究中，使用了计算反应发现工具来彻底搜索化学空间中可行的二聚化和噻吩格氏试剂配体交换的途径。发现三个桥接的二聚体，μ-（Cl，C），μ-（Cl，Cl）和μ-Cl是重要的中间体，它们通过涉及噻吩基团的π相互作用而稳定。
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