Explaining the Advantageous Impact of Tertiary versus Secondary Nitrogen Center on the Activity of PNP‐Pincer Co(I)‐Complexes for Catalytic Hydrogenation of CO 2

Autor:	Swapan K. Pati, Neha Bothra, Shubhajit Das
Rok vydání:	2021
Předmět:	Reaction mechanism Hydride Organic Chemistry chemistry.chemical_element General Chemistry Medicinal chemistry Nitrogen Catalysis Pincer movement chemistry.chemical_compound chemistry lipids (amino acids peptides and proteins) Dehydrogenation Formate Pincer ligand
Zdroj:	Chemistry – A European Journal. 27:16407-16414
ISSN:	1521-3765 0947-6539
Popis:	Pincer ligated coordination complexes of base metals have shown remarkable catalytic activity for hydrogenation/dehydrogenation of CO2 . The recently reported MeN[CH2 CH2 (i Pr2 )]2 Co(I)PNP-pincer complex was shown to exhibit substantially higher catalytic activity in comparison to the corresponding catalyst, HN[CH2 CH2 (i Pr2 )]2 Co(I)PNP, bearing a secondary nitrogen center on the pincer ligand. Here, we computationally investigate the mechanisms for hydrogenation of CO2 to formate catalyzed by these two Co-PNP complexes to explain how such a small structural difference could have a sizable impact on their catalytic activity. Plausible hydrogenation routes were examined in details and our findings provide solid support for the experimental observations. Our results reveal that such trends in catalytic activity could be explained from the lower activation barrier for the hydride transfer step upon changing the pincer nitrogen center from secondary to tertiary.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::17d6bf2274d81fa424eb3eb337b0174d https://doi.org/10.1002/chem.202102386 Zobrazit plný text záznamu Plný text ve formátu PDF