Syntheses, Structures, and Reactivity of NHC Copper(I) Boryl Complexes: A Systematic Study
Syntheses, Structures, and Reactivity of NHC Copper(I) Boryl Complexes: A Systematic Study
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DOI：
10.1021/acs.organomet.8b00672
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发表时间：
2018-11-12
期刊：
影响因子：
2.8
通讯作者：
Borner, Corinna
中科院分区：
文献类型：
--
作者：
Kleeberg, Christian;Borner, Corinna
以对称的四烷氧基和不对称的二烷氧基二氨基二硼烷(4)为原料，通过B-B活化，通过Sigma键歧化反应合成了5种新型的NHC铜(I)硼配合物。尽管它们的稳定性较低，但NHC铜硼络合物的光谱和结构得到了全面的表征。NHC配体(ItBu或Me(2)Iipr)以及硼基配体(Bpin、Bdmab或BiPrEn)的变化首次允许在这种络合物中系统地研究对空间阻碍的依赖。对于空间要求较高的配体组合，得到了单核线性配合物，而对于要求较低的配体组合，得到了具有两个桥联钼硼配体的二聚双核配合物，表现出极短的铜中心点铜距离(
Five novel NHC copper(I) boryl complexes were synthesized by B-B activation via sigma-bond metathesis of symmetrical tetraalkoxy and unsymmetrical dialkoxy diamino diborane(4) derivatives. Despite their low stability, the NHC copper boryl complexes were thoroughly characterized spectroscopically and structurally. Variation of the NHC ligand (ItBu or Me(2)IiPr) as well as of the boryl ligand (Bpin, Bdmab, or BiPrEn) allowed, for the first time systematically, a study in such complexes of the dependence on steric encumbrance. For sterically more demanding ligand combinations, mononuclear linear complexes were obtained, while with less demanding ligand combinations, dimeric dinuclear complexes with two bridging mu-boryl ligands were obtained, exhibiting extremely short Cu center dot center dot center dot Cu distances (