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Title: Reduction of CO2 to methanol using aluminum ester FLPs

Abstract

Herein we report the synthesis of Al-based esters containing halogenated benzene rings. These Lewis acids were paired with phosphines to form frustrated Lewis pairs (FLPs) which could subsequently bind CO2. While these FLPs were not sufficiently water-stable to catalyze the reduction of CO2 to MeOH using NH3BH3 as the reductant, we examine the effect of varying Lewis acid strength. Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases where the acid and base are either sterically or geometrically restricted from interacting as strongly as their electronic structures would allow. This effect leads to enhanced reactivity towards small molecules and, consequently, interest in their potential as metal-free catalysts [1], [2], [3], [4] and [5]. Furthermore, to-date, the biggest success has been based around the ability of a myriad of systems to heterolytically cleave H2 and perform catalytic hydrogenations [2] and [3].

Authors:
 [1];  [2];  [2];  [2];  [2];  [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. The Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1329898
Alternate Identifier(s):
OSTI ID: 1780435
Report Number(s):
LA-UR-15-26338
Journal ID: ISSN 1387-7003
Grant/Contract Number:  
AC52-06NA25396; LDRD 20120197ER
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry Communications
Additional Journal Information:
Journal Volume: 61; Journal Issue: C; Journal ID: ISSN 1387-7003
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; inorganic and physical chemistry; frustrated Lewis pair; CO2; MeOH; ammonia borane

Citation Formats

Smythe, Nathan C., Dixon, David A., Garner, III, Edward B., Rickard, Meredith M., Mendez, Mariano, Scott, Brian Lindley, Zelenay, Barbara, and Sutton, Andrew D. Reduction of CO2 to methanol using aluminum ester FLPs. United States: N. p., 2015. Web. doi:10.1016/j.inoche.2015.10.009.
Smythe, Nathan C., Dixon, David A., Garner, III, Edward B., Rickard, Meredith M., Mendez, Mariano, Scott, Brian Lindley, Zelenay, Barbara, & Sutton, Andrew D. Reduction of CO2 to methanol using aluminum ester FLPs. United States. https://doi.org/10.1016/j.inoche.2015.10.009
Smythe, Nathan C., Dixon, David A., Garner, III, Edward B., Rickard, Meredith M., Mendez, Mariano, Scott, Brian Lindley, Zelenay, Barbara, and Sutton, Andrew D. Fri . "Reduction of CO2 to methanol using aluminum ester FLPs". United States. https://doi.org/10.1016/j.inoche.2015.10.009. https://www.osti.gov/servlets/purl/1329898.
@article{osti_1329898,
title = {Reduction of CO2 to methanol using aluminum ester FLPs},
author = {Smythe, Nathan C. and Dixon, David A. and Garner, III, Edward B. and Rickard, Meredith M. and Mendez, Mariano and Scott, Brian Lindley and Zelenay, Barbara and Sutton, Andrew D.},
abstractNote = {Herein we report the synthesis of Al-based esters containing halogenated benzene rings. These Lewis acids were paired with phosphines to form frustrated Lewis pairs (FLPs) which could subsequently bind CO2. While these FLPs were not sufficiently water-stable to catalyze the reduction of CO2 to MeOH using NH3BH3 as the reductant, we examine the effect of varying Lewis acid strength. Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases where the acid and base are either sterically or geometrically restricted from interacting as strongly as their electronic structures would allow. This effect leads to enhanced reactivity towards small molecules and, consequently, interest in their potential as metal-free catalysts [1], [2], [3], [4] and [5]. Furthermore, to-date, the biggest success has been based around the ability of a myriad of systems to heterolytically cleave H2 and perform catalytic hydrogenations [2] and [3].},
doi = {10.1016/j.inoche.2015.10.009},
journal = {Inorganic Chemistry Communications},
number = C,
volume = 61,
place = {United States},
year = {Fri Oct 09 00:00:00 EDT 2015},
month = {Fri Oct 09 00:00:00 EDT 2015}
}

Journal Article:

Citation Metrics:
Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: X-Ray crystal structure of PPh3-(Cl-3) with hydrogen atoms omitted and 50% thermal ellipsoids.

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Works referencing / citing this record:

Diphosphination of CO 2 and CS 2 mediated by frustrated Lewis pairs – catalytic route to phosphanyl derivatives of formic and dithioformic acid
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