Synthesis and molecular structural studies of racemic chiral-at-vanadium(<scp>v</scp>) complexes using an unsymmetric achiral phenolic bidentate ligand
Synthesis and molecular structural studies of racemic chiral-at-vanadium(<scp>v</scp>) complexes using an unsymmetric achiral phenolic bidentate ligand
复制标题
使用不对称非手性酚类二齿配体合成外消旋手性钒(<scp>v</scp>)配合物并进行分子结构研究
DOI：
10.1039/d2dt03436k
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发表时间：
2023
影响因子：
4
通讯作者：
Shionoya Mitsuhiko
中科院分区：
文献类型：
--
作者：
Nagata Koichi;Hino Ayako;Ube Hitoshi;Sato Hiroyasu;Shionoya Mitsuhiko
使用不对称非手性酚二齿化合物，将单核氧钒(V)络合物[V(O)XL (1: X = Ot-Bu, 2: X = Cl)] [H2L: 2,2'-亚甲基双(4,6-二叔丁基苯酚)(4'-叔丁基-6'-(1-金刚烷基)苯酚)]合成为外消旋化合物，用于不对称催化配体（H2L）、核磁共振和紫外-可见吸收光谱、单晶X射线衍射和红外光谱揭示了它们在溶液和晶体中的外消旋手性钒结构。此外，理论计算表明，不对称配体的HOMO-LUMO能隙较小，这促进了金属中心的d轨道分裂。
Mononuclear oxovanadium(V) complexes [V(O)XL (1: X = Ot-Bu, 2: X = Cl)] [H2L: 2,2′-methylene bis(4,6-di-tert-butylphenol)(4′-tert-butyl-6′-(1-adamantyl)phenol)] directed towards asymmetric catalysis have been synthesised as racemic compounds using an unsymmetric and achiral phenolic bidentate ligand (H2L), and NMR and UV-vis absorption spectroscopies, single-crystal X-ray diffraction, and IR spectroscopy revealed their racemic chiral-at-vanadium structures in solution and in the crystal. In addition, theoretical calculations revealed that the HOMO–LUMO energy gap is smaller for unsymmetric ligands, which promotes d-orbital splitting of the metal centre.