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Title: Acceleration of CO 2 insertion into metal hydrides: ligand, Lewis acid, and solvent effects on reaction kinetics

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC02535E· OSTI ID:1460464
 [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Yale University, New Haven, USA
  2. Department of Chemistry, University of Missouri, Columbia, USA
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The insertion of CO2 into metal hydrides and the microscopic reverse decarboxylation of metal formates are important elementary steps in catalytic cycles for both CO2 hydrogenation to formic acid and methanol as well as formic acid and methanol dehydrogenation. Here, we use rapid mixing stopped-flow techniques to study the kinetics and mechanism of CO2 insertion into transition metal hydrides. The investigation finds that the most effective method to accelerate the rate of CO2 insertion into a metal hydride can be dependent on the nature of the rate-determining transition state (TS). We demonstrate that for an innersphere CO2 insertion reaction, which is proposed to have a direct interaction between CO2 and the metal in the rate-determining TS, the rate of insertion increases as the ancillary ligand becomes more electron rich or less sterically bulky. There is, however, no rate enhancement from Lewis acids (LA). In comparison, we establish that for an outersphere CO2 insertion, proposed to proceed with no interaction between CO2 and the metal in the rate-determining TS, there is a dramatic LA effect. Furthermore, for both inner- and outersphere reactions, we show that there is a small solvent effect on the rate of CO2 insertion. Solvents that have higher acceptor numbers generally lead to faster CO2 insertion. Our results provide an experimental method to determine the pathway for CO2 insertion and offer guidance for rate enhancement in CO2 reduction catalysis.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Yale Univ., New Haven, CT (United States); Univ. of Missouri, Columbia, MO (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Inst. of Health (NIH) (United States)
Grant/Contract Number:
SC0018222; SC0001059; CHE-1150826; GM050422
OSTI ID:
1460464
Alternate ID(s):
OSTI ID: 1505499
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 32; ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 41 works
Citation information provided by
Web of Science

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Cited By (3)

Isolation of the Metalated Ylides [Ph 3 P−C−CN]M (M=Li, Na, K): Influence of the Metal Ion on the Structure and Bonding Situation journal January 2019
Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies: Carbon Dioxide Insertion into Bridging Iron Hydrides: Kinetic and Mechanistic Studies journal February 2019
Synthesis of porous coordination polymers using carbon dioxide as a direct source journal January 2019

Figures / Tables (16)

Fig. 1(p. 2)figure Fig. 1
Scheme 1(p. 2)figure Scheme 1
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Table 1(p. 3)table Table 1
Fig. 4(p. 4)figure Fig. 4
Table 2(p. 4)table Table 2
Scheme 2(p. 5)figure Scheme 2
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Fig. 5(p. 7)figure Fig. 5
Table 5(p. 7)table Table 5
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Fig. 7(p. 8)figure Fig. 7
Table 6(p. 8)table Table 6

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