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Zr vs. Ti molecular and silica-supported imido complexes in stoichiometric and catalytic oxo/imido heterometathesis

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 heterogeneous catalysts and discover new reactivities and catalytic transformations. SOMC relies on...

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Bibliographic Details
Published in:Inorganic chemistry frontiers 2023-09, Vol.10 (18), p.5357-5370
Main Authors: Pichugov, Andrey V, Rumyantsev, Andrey V, Bushkov, Nikolai S, Zhizhin, Anton A, Dmitry Yu Aleshin, Talanova, Valeria N, Takazova, Rina U, Trummer, David, Mance, Deni, Zhizhko, Pavel A, Zarubin, Dmitry N
Format: Article
Language:English
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Summary: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 heterogeneous 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)(Me2Pyr)2(py)2 (R = tBu (1a), Ar (1b); Ar = 2,6-iPr2C6H3, Me2Pyr = 2,5-dimethylpyrrolyl, py = pyridine), investigate their grafting onto the surface of partially dehydroxylated silica and evaluate the obtained materials as oxo/imido heterometathesis catalysts 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)(Me2Pyr)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.
ISSN:2052-1545
2052-1553
DOI:10.1039/d3qi00735a