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Article Abstract
The rotation frequencies of amido ligands are highly sensitive to the electronic structure of 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.
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| http://dx.doi.org/10.1021/acs.inorgchem.5c02067 | DOI Listing |
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