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Analyses of the Structural and Electronic Properties of NHCs with Bicyclic Architectures
Organometallics ( IF 2.5 ) Pub Date : 2020-10-27 , DOI: 10.1021/acs.organomet.0c00564 Shin Ando 1 , Mio Otsuka 1 , Tadao Ishizuka 1
Organometallics ( IF 2.5 ) Pub Date : 2020-10-27 , DOI: 10.1021/acs.organomet.0c00564 Shin Ando 1 , Mio Otsuka 1 , Tadao Ishizuka 1
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Quantification of the steric and electronic properties of ligands is an important task for the development of highly effective chemical transformations when using a metal complex as a catalyst. In this study, we used silver and iridium complexes to perform systematic analyses to quantify the steric and electronic properties of original NHCs, which we refer to as DHASI and BCPSI. In addition to two silver chloride complexes that we previously reported, two novel BCPSIiPrAgCl and BCPSICyAgCl complexes were prepared and used for XRD studies to quantify the steric properties via use of a method referred to as the percent buried volume (%VBur). We then synthesized 6 IrCl(CO)2(HNC) complexes to calculate the TEP values, and the results indicated that the influences of two different core bicyclic motifs were somewhat unclear, while the influences of different N-substituents were readily apparent. Finally, the original NHCs were applied to a copper catalyzed allylic arylation of cinnamyl bromide with PhMgBr. The regioselectivity of the substitutions suggested that the steric environments existing at relatively long distances from the bound copper also exerted a considerable amount of influence over the catalytic properties.
中文翻译：
具有双环结构的NHC的结构和电子性质分析
当使用金属络合物作为催化剂时，对配位体的空间和电子性质进行定量是开发高效化学转化的重要任务。在这项研究中，我们使用银和铱配合物进行系统分析，以量化原始NHC的空间和电子性质，我们将其称为DHASI和BCPSI。除了我们先前报道的两种氯化银配合物外，还制备了两种新型的BCPSIiPrAgCl和BCPSICyAgCl配合物，并用于XRD研究，通过使用一种称为掩埋体积百分比（％V Bur）的方法来量化空间特性。然后合成6 IrCl（CO）2（HNC）配合物计算TEP值，结果表明，两个不同的核心双环基序的影响尚不清楚，而不同的N-取代基的影响则显而易见。最后，将原始的NHC应用于铜催化的肉桂基溴化物与PhMgBr的烯丙基芳基化反应。取代的区域选择性表明，距键合铜相对较长距离的空间环境也对催化性能产生了相当大的影响。
更新日期：2020-11-09
中文翻译：
具有双环结构的NHC的结构和电子性质分析
当使用金属络合物作为催化剂时，对配位体的空间和电子性质进行定量是开发高效化学转化的重要任务。在这项研究中，我们使用银和铱配合物进行系统分析，以量化原始NHC的空间和电子性质，我们将其称为DHASI和BCPSI。除了我们先前报道的两种氯化银配合物外，还制备了两种新型的BCPSIiPrAgCl和BCPSICyAgCl配合物，并用于XRD研究，通过使用一种称为掩埋体积百分比（％V Bur）的方法来量化空间特性。然后合成6 IrCl（CO）2（HNC）配合物计算TEP值，结果表明，两个不同的核心双环基序的影响尚不清楚，而不同的N-取代基的影响则显而易见。最后，将原始的NHC应用于铜催化的肉桂基溴化物与PhMgBr的烯丙基芳基化反应。取代的区域选择性表明，距键合铜相对较长距离的空间环境也对催化性能产生了相当大的影响。
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