Secondary Coordination Sphere Design to Modify Transport of Protons and CO 2
An exploration of secondary coordination sphere (SCS) functional groups is presented here with a focus on proton transport to a metal hydride active site for H 2 formation and transport of CO 2 so that formate can be obtained. In MeCN–H 2 O, p K a (AH) and steric bulk of the SCS groups are discussed...
Published in: | Inorganic Chemistry |
---|---|
Main Authors: | , |
Language: | unknown |
Published: |
2021
|
Subjects: | |
Online Access: | http://www.osti.gov/servlets/purl/1657670 https://www.osti.gov/biblio/1657670 https://doi.org/10.1021/acs.inorgchem.9b03102 |
Summary: | An exploration of secondary coordination sphere (SCS) functional groups is presented here with a focus on proton transport to a metal hydride active site for H 2 formation and transport of CO 2 so that formate can be obtained. In MeCN–H 2 O, p K a (AH) and steric bulk of the SCS groups are discussed along with their influence on each step in the mechanism for CO 2 to formate catalysis and along with the influence of the proton source, which is MeCN–H 2 O or (MeCN) 2 H 2 O in MeCN–H 2 O (95:5) under N 2 atmosphere. Under CO 2 , carbonic acid is also available. Catalysts containing various SCS groups were synthesized from [Fe 4 N(CO) 12 ] – and have the form [Fe 4 N(CO) 11 L] – where L is Ph 2 P-SCS. Hydride formation rates are distinct under N 2 versus CO 2 , and that variation is dependent on the size of the SCS group. Under CO 2 , larger SCS groups inhibit access of the MeCN–H 2 O adducts to the active site and formate formation is observed, whereas smaller SCS groups allow transport of these adducts. This is best illustrated by catalysts containing the small SCS group pyridyl and the large SCS group N , N -dimethylaniline which both have the same p K a (AH) value. The smaller pyridyl group promotes selective H 2 evolution, whereas larger N , N -dimethylaniline supports selective formate formation by slowing the transport of large MeCN–H 2 O adducts, allowing hydride transfer to the smaller substrate CO 2 . |
---|