Pavel Zhizhko


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Zhizhko

First Name

Pavel

ORCID

0000-0001-5026-8150

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  • Zr vs. Ti molecular and silica-supported imido complexes in stoichiometric and catalytic oxo/imido heterometathesis
    Item type: Journal Article
    Pichugov, Andrey V.; Rumyantsev, Andrey V.; Bushkov, Nikolai S.; et al. (2023)
    Inorganic Chemistry Frontiers
    Surface Organometallic Chemistry (SOMC) aims at selective preparation of unusual or highly reactive species on the surfaces of inorganic supports in order to reach a better understanding of classical hetero-geneous catalysts and discover new reactivities and catalytic transformations. SOMC relies on the application of both surface science techniques and molecular organometallic chemistry; in particular it requires rational design of the molecular precursors to ensure their selective reactivity with the supports. In this report we apply the SOMC protocols to prepare well-defined silica-supported Zr imido complexes. We describe the synthesis of Zr imido pyrrolyl complexes Zr(=NR)(Me(2)Pyr)(2)(py)2 (R = tBu (1a), Ar (1b); Ar = 2,6-iPr(2)C(6)H(3), Me(2)Pyr = 2,5-dimethylpyrrolyl, py = pyridine), investigate their grafting onto the surface of partially dehydroxylated silica and evaluate the obtained materials as oxo/imido heterometathesis cata-lysts in comparison with the previously reported highly active supported Ti systems. We also investigate the stoichiometric oxo/imido exchange reactivity of Zr imides using Ph2CO as a probe molecule, compare them with isostructural Ti analogs Ti(=NR)(Me(2)Pyr)(2)(py)(2 )(R = tBu (2a), Ar (2b)), and discuss how these results correlate with the differences in their electronic structure and catalytic performance of silica-supported species.
Publications 1 - 1 of 1