The Role of L‐Ligands in Silica‐Supported Ti Oxo/Imido Heterometathesis Catalysts

ABSTRACT We report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=N t Bu)(Me 2 Pyr)(py) 2 ( 1s ), where py is replaced with stronger electron‐donating 4‐( N,N‐ dimethylamino)pyridine ( 2s ) or bidentate 2,2′‐bipyridine ( 3s ). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.

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Publication Details

Journal
Applied Organometallic Chemistry
Published
2024-09-26
DOI
https://doi.org/10.1002/aoc.7746
Primary Topic
Synthetic Organic Chemistry Methods
Type
article
Field-Weighted Citation Impact
0.00

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article

The Role of L‐Ligands in Silica‐Supported Ti Oxo/Imido Heterometathesis Catalysts

D. Kh. Kitaeva, Anton A. Zhizhin, Andrey V. Pichugov, Р. У. Таказова et al.
Applied Organometallic Chemistry
Synthetic Organic Chemistry Methods
article

The Role of L‐Ligands in Silica‐Supported Ti Oxo/Imido Heterometathesis Catalysts

D. Kh. Kitaeva, Anton A. Zhizhin, Andrey V. Pichugov, Р. У. Таказова, Dmitry Yu. Aleshin, Dmitry N. Zarubin, Evgenii I. Gutsul, Nikolai S. Bushkov, Роман А. Новиков, Andrey V. Rumyantsev, Pavel A. Zhizhko, F.M. Dolgushin
article en

Abstract

ABSTRACT We report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=N t Bu)(Me 2 Pyr)(py) 2 ( 1s ), where py is replaced with stronger electron‐donating 4‐( N,N‐ dimethylamino)pyridine ( 2s ) or bidentate 2,2′‐bipyridine ( 3s ). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.

Applied Organometallic ChemistryVol. 38(12)
Lomonosov Moscow State University (RU), A. N. Nesmeyanov Institute of Organoelement Compounds (RU), N.D. Zelinsky Institute of Organic Chemistry (RU), NS Kurnakova Institute of General and Inorganic Chemistry (RU)
Russian Science Foundation, Ministry of Science and Higher Education of the Russian Federation, Russian Academy of Sciences
Openalex Percentile: Top 88%
Synthetic Organic Chemistry Methods
DOIOpen Access PDFOpenAlex
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