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苊-1,2-二亚胺钛配合物中配体诱导的分子内氧化还原多样性

Ligand-Induced Intramolecular Redox Diversity in Titanium Complexes with Acenaphthene-1,2-diimine.

作者信息

Morozov Alexander G, Dodonov Vladimir A, Rychagova Elena A, Ketkov Sergey Yu, Fedushkin Igor L

机构信息

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences (IOMC RAS), Tropinina 49, Nizhny Novgorod 603950, Russian Federation.

出版信息

Inorg Chem. 2024 Mar 11;63(10):4657-4668. doi: 10.1021/acs.inorgchem.3c04250. Epub 2024 Feb 24.

DOI:10.1021/acs.inorgchem.3c04250
PMID:38401059
Abstract

A series of the chlorido and alkoxychlorido titanium complexes of the general formula (dpp-Bian)Ti(OPr)Cl, where dpp-Bian = 1,2-bis[(2,6-PrCH)imino]acenaphthene = 0 (), 1 (), 2 (), as well as (dpp-Bian)Ti(OPr) () and (dpp-Bian)Ti(OPr)Cl (), were isolated and characterized using single-crystal X-ray diffraction analysis and spectroscopic studies combined with density functional theory (DFT) calculations. In the solid state, compounds reveal a square-pyramidal geometry at the metal center supported with monoanionic dpp-Bian, whereas with a neutral diimine ligand and bearing a dianionic enebisamide dpp-Bian show, respectively, an octahedral and tetrahedral coordination surrounding the metal ion. Paramagnetic complexes exhibit electron paramagnetic resonance spectra in both toluene solution and solid state, confirming the transfer of spin density from the metal ion to the dpp-Bian ligand as the number of alkoxy groups increases. The increase in polarity of the Ti-N bonds in the row < < contributes to enhanced stability of the metal complexes with respect to O-donor molecules. Thus, in tetrahydrofuran (THF), compounds and undergo reversible solvolysis, whereas complex is stable. The charge and spin density distributions as well as molecular orbital energies in were analyzed on the basis of DFT calculations which also provided information on the electronic transition energies, absorption band assignments, and thermodynamic parameters of the reactions between the complexes and THF.

摘要

一系列通式为(dpp - Bian)Ti(OPr)Cl的氯代和烷氧基氯代钛配合物,其中dpp - Bian = 1,2 - 双[(2,6 - PrCH)亚氨基]苊烯(分别为 = 0 ()、1 ()、2 ()),以及(dpp - Bian)Ti(OPr) ()和(dpp - Bian)Ti(OPr)Cl (),通过单晶X射线衍射分析、光谱研究并结合密度泛函理论(DFT)计算进行了分离和表征。在固态下,化合物 在单阴离子dpp - Bian的支撑下,金属中心呈现出四方锥几何构型,而 带有中性二亚胺配体, 带有双阴离子烯二酰胺dpp - Bian,分别显示出围绕金属离子的八面体和四面体配位。顺磁性配合物 在甲苯溶液和固态中均表现出电子顺磁共振光谱,证实随着烷氧基数量的增加,自旋密度从金属离子转移到dpp - Bian配体上。在 < < 序列中Ti - N键极性的增加有助于金属配合物相对于氧供体分子的稳定性增强。因此,在四氢呋喃(THF)中,化合物 和 发生可逆溶剂解,而配合物 是稳定的。基于DFT计算分析了 中的电荷和自旋密度分布以及分子轨道能量,该计算还提供了关于电子跃迁能量、吸收带归属以及配合物与THF之间反应的热力学参数的信息。

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