Ultra-Confined Environments May Restrict the Possible Configurations of Supported Metal Complexes.

IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Frédéric A Perras, Rashmi Jena, Sazia Sultana, M Matiar Rahman, Simin Sun, Sayak Banerjee, Scott A Southern, Aaron D Sadow, Wenyu Huang, Aaron L Odom
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引用次数: 0

Abstract

The rotation frequencies of amido ligands are highly sensitive to the electronic structure of d0 transition metal complexes and have been used to study ligand donor properties. While attempting to study the donor properties of silanolate ligands in a silica-supported Cr complex, we observed highly restricted motions due to the added steric hindrance from the support, with only approximately half of the amides rotating on a 50 ms time scale. Surprisingly, when the same species is grafted into narrow 2.2 nm pores, all amido ligands are able to rotate. Density functional theory calculations suggest that confinement may limit the possible coordination sites and the configuration of the formed surface species, potentially enabling the formation of conformationally homogeneous surface site populations.

超密闭环境可能限制支撑金属配合物的可能构型。
氨基配体的旋转频率对过渡金属配合物的电子结构高度敏感,并已被用于研究配体供体的性质。在试图研究硅酸盐配体在二氧化硅支撑的Cr配合物中的供体性质时,我们观察到由于支撑物增加的空间位阻,运动受到高度限制,只有大约一半的酰胺在50 ms的时间尺度上旋转。令人惊讶的是,当同一物种被接枝到2.2 nm的狭窄孔中时,所有的氨基配体都能够旋转。密度泛函理论计算表明,约束可能会限制可能的配位位点和形成的表面物种的配置,从而可能形成构象均匀的表面位点群。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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