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Poly(ethyleneimine)‐Mediated Consecutive Hydrogenation of Carbon Dioxide to Methanol with Ru Catalysts
Author(s) -
Yoshimura Atsuki,
Watari Ryo,
Kuwata Shigeki,
Kayaki Yoshihito
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900322
Subject(s) - chemistry , methanol , catalysis , formamides , ethyleneimine , formic acid , moiety , formamide , polymer chemistry , amine gas treating , piperidine , organic chemistry , pincer movement , polymer
The utilization of polymeric amines for the hydrogenation of CO 2 to methanol via formamides was explored with a focus on a catalytic promoter, as well as a beneficial reaction medium with enhanced basicity. Branched and linear poly(ethyleneimine)s (PEIs) were efficiently formylated in the presence of a series of PN H P‐pincer Ru complexes under CO 2 hydrogenation conditions at 100 °C in THF. The obtained N ‐formylated PEI was characterized by NMR spectroscopy. The formamide units on the polymer were reduced at a higher temperature under pressurized H 2 to afford methanol and to recover the starting PEI. Moreover, PEI was optimally utilized for a one‐pot synthesis of methanol catalyzed by Ru–PN H P pincer complexes. The resulting polymer can be separated from the reaction mixture to afford methanol without the contamination of formic acid derivatives in the liquid phase. Under optimized reaction conditions of 2.0 MPa of CO 2 and 6.0 MPa of H 2 at 150 °C, methanol was successfully obtained with a turnover number (TON) up to 689, and the amine moiety can be used catalytically.