English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Cobalt-Catalyzed Hydrosilylation of Carbon Dioxide to the Formic Acid, Formaldehyde, and Methanol Level—How to Control the Catalytic Network?

Cramer, H. H., Ye, S., Neese, F., Werlé, C., & Leitner, W. (2021). Cobalt-Catalyzed Hydrosilylation of Carbon Dioxide to the Formic Acid, Formaldehyde, and Methanol Level—How to Control the Catalytic Network? JACS Au, 1(11), 2058-2069. doi:10.1021/jacsau.1c00350.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files
hide Files
:
au1c00350_si_001.pdf (Supplementary material), 3MB
Name:
au1c00350_si_001.pdf
Description:
Supporting Information
Visibility:
Public
MIME-Type / Checksum:
application/pdf / [MD5]
Technical Metadata:
Copyright Date:
-
Copyright Info:
-
License:
-

Locators

show

Creators

show
hide
 Creators:
Cramer, Hanna H.1, 2, Author              
Ye, Shengfa3, 4, Author              
Neese, Frank5, Author              
Werlé, Christophe6, 7, Author              
Leitner, Walter1, 2, Author              
Affiliations:
1Research Department Leitner, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023872              
2Institut für Technische und Makromolekulare Chemie (ITMC), RWTH Aachen University, Worringer Weg 2, 52074 Aachen, Germany, ou_persistent22              
3State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China, ou_persistent22              
4Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              
5Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
6Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023874              
7Ruhr University Bochum, Universitätsstr. 150, 44801 Bochum, Germany, ou_persistent22              

Content

show
hide
Free keywords: -
 Abstract: The selective hydrosilylation of carbon dioxide (CO2) to either the formic acid, formaldehyde, or methanol level using a molecular cobalt(II) triazine complex can be controlled based on reaction parameters such as temperature, CO2 pressure, and concentration. Here, we rationalize the catalytic mechanism that enables the selective arrival at each product platform. Key reactive intermediates were prepared and spectroscopically characterized, while the catalytic mechanism and the energy profile were analyzed with density functional theory (DFT) methods and microkinetic modeling. It transpired that the stepwise reduction of CO2 involves three consecutive catalytic cycles, including the same cobalt(I) triazine hydride complex as the active species. The increasing kinetic barriers associated with each reduction step and the competing hydride transfer steps in the three cycles corroborate the strong influence of the catalyst environment on the product selectivity. The fundamental mechanistic insights provide a consistent description of the catalytic system and rationalize, in particular, the experimentally verified opportunity to steer the reaction toward the formaldehyde product as the chemically most challenging reduction level.

Details

show
hide
Language(s): eng - English
 Dates: 2021-08-122021-10-042021-11-22
 Publication Status: Published in print
 Pages: 282
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacsau.1c00350
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: JACS Au
  Abbreviation : JACS Au
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: 11 Volume / Issue: 1 (11) Sequence Number: - Start / End Page: 2058 - 2069 Identifier: ISSN: 2691-3704
CoNE: https://pure.mpg.de/cone/journals/resource/2691-3704