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Stereoisomerism as an Origin of Different Reactivity of Ir(III) PC(sp3)P Pincer Catalystsстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 3 марта 2021 г.
- Авторы: Kirkina Vladislava, Silantyev Gleb, De-botton Sophie, Filippov Oleg, Titova Ekaterina, Pavlov Alexander, Belkova Natalia, Epstein Lina, Gelman Dmitri, Shubina Elena
- Журнал: Inorganic Chemistry
- Том: 59
- Номер: 17
- Год издания: 2020
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 11962
- Последняя страница: 11975
- DOI: 10.1021/acs.inorgchem.0c00797
- Аннотация: Two stereoisomers of pentacoordinate iridium(III) hydridochloride with triptycene-based PC(sp3)P pincer ligand (1,8-bis(diisopropylphosphino)triptycene), 1 and 2, differ by the orientation of hydride ligand relative to the bridgehead ring of triptycene. According to DFT/B3PW91/def2-TZVP calculations performed, an equatorial Cl ligand can relatively easily change its position in 1, whereas that is not the case in 2. Both complexes 1 and 2 readily bind the sixth ligand to protect the empty coordination site. Variable temperature spectroscopic (NMR, IR, and UV–visible) studies show the existence of two isomers of hexacoordinate complexes 1·MeCN, 2·MeCN, and 2·Py with acetonitrile or pyridine coordinated trans to hydride or trans to metalated C(sp3), whereas only the equatorial isomer is found for 1·Py. These complexes are stabilized by various intramolecular noncovalent C–H···Cl interactions that are affected by the rotation of isopropyls or pyridine. The substitution of MeCN by pyridine is slow yielding axial Py complexes as kinetic products and the equatorial Py complexes as thermodynamic products with faster reactions of 1·L. Ultimately, that explains the higher activity of 1 in the catalytic alkenes’ isomerization observed for allylbenzene, 1-octene, and pent-4-enenitrile, which proceeds as an insertion/elimination sequence rather than through the allylic mechanism.
- Добавил в систему: Киркина Владислава Александровна
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