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二膦基硼烷配合物中 Pd→B 相互作用的评估及其对内向还原消除的影响。

Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner-Sphere Reductive Elimination.

机构信息

Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1A, 52074, Aachen, Germany.

出版信息

Chemistry. 2020 Oct 21;26(59):13436-13444. doi: 10.1002/chem.202001189. Epub 2020 Sep 18.

DOI:10.1002/chem.202001189
PMID:32428264
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7692930/
Abstract

The dative Pd→B interaction in a series of DPB Pd and Pd complexes ( DPB =(o-PR C H ) BR', diphosphinoborane) was analyzed using XRD, B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state Pd and Pd , stabilizing the latter. Reaction of lithium amides with [( DPB )Pd (4-NO C H )I] chemoselectively yields the C-N coupling product. DFT modelling indicates no significant impact of Pd →B coordination on the inner-sphere reductive elimination rate.

摘要

使用 XRD、B NMR 光谱和 NBO/NLMO 计算分析了一系列 DPB Pd 和 Pd 配合物中供体 Pd→B 相互作用（DPB =(o-PR C H ) BR'，二膦硼烷）。硼烷受体可以区分氧化态 Pd 和 Pd ，稳定后者。锂酰胺与 [(DPB)Pd(4-NO C H )I] 的反应具有化学选择性，生成 C-N 偶联产物。DFT 建模表明 Pd→B 配位对分子内还原消除速率没有显著影响。

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