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Title: Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction

Journal Article · · ACS Catalysis
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States
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The hydricity ΔG°H- of a metal hydride is an important parameter for describing the reactivity of such complexes. Here, we compile a comprehensive data set consisting of 51 transition-metal hydride complexes [M-H](n-1)+ with known ΔG°H- values in acetonitrile for which the one-electron reduction of the parent complex [M]n+ is reversible. Plotting the hydricity as a function of respective E1/2(Mn+/(n-1)+) yields a robust linear correlation. While this correlation has been previously noted for limited data sets, our analysis demonstrates that this trend extends over a wide range of metal identities, ligand architectures, structural geometries, and overall charges of the metal hydride. This correlation is modeled using established thermochemical cycles relating the hydricity and homolytic bond free energy of the metal-hydride bond. The linear trend of the model enables the estimation of hydricity simply on the basis of the reduction potential of the parent complex and thus provides a guide for the rational design and tuning of metal hydride catalysts for small-molecule reduction, such as CO2 to formic acid.

Research Organization:
Univ. of California, San Diego, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0004993
OSTI ID:
1417924
Alternate ID(s):
OSTI ID: 1508329
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Vol. 8 Journal Issue: 2; ISSN 2155-5435
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 135 works
Citation information provided by
Web of Science

Cited By (14)

Role of Ligand in the Selective Production of Hydrogen from Formic Acid Catalysed by the Mononuclear Cationic Zinc Complexes [(L)Zn(H)] + (L=tpy, phen, and bpy) journal July 2019
Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity journal August 2019
A look at periodic trends in d-block molecular electrocatalysts for CO 2 reduction journal January 2019
Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts journal January 2019
Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand journal June 2019
Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential journal March 2020
Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential journal February 2020
Making a Splash in Homogeneous CO 2 Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms journal July 2018
Hydride Pinning Pathway in the Hydrogenation of CO 2 to Formic Acid on Dimeric Tin Dioxide journal February 2019
Diverse Catalytic Systems and Mechanistic Pathways for Hydrosilylative Reduction of CO 2 journal September 2019
Unambiguous hydrogenation of CO 2 by coinage-metal hydride anions: an intuitive idea based on in silico experiments journal January 2019
Thermodynamic targeting of electrocatalytic CO 2 reduction: advantages, limitations, and insights for catalyst design journal January 2019
Bulk gold catalyzes hydride transfer in the Cannizzaro and related reactions journal January 2019
[Re(η 6 -arene) 2 ] + as a highly stable ferrocene-like scaffold for ligands and complexes journal January 2020

Figures / Tables (19)

Scheme 1(p. 1)figure Scheme 1
Scheme 2(p. 2)figure Scheme 2
Table 1(p. 2)table Table 1
Table 2(p. 3)table Table 2
Table 3(p. 3)table Table 3
Figure 1(p. 4)figure Figure 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 5)figure Figure 3
Scheme 3(p. 5)figure Scheme 3
Figure 4(p. 6)figure Figure 4
Figure 5(p. 6)figure Figure 5
Figure 6(p. 7)figure Figure 6
Scheme 4(p. 7)figure Scheme 4
Scheme 5(p. 7)figure Scheme 5
Figure 7(p. 8)figure Figure 7
Scheme 6(p. 8)figure Scheme 6
Scheme 7(p. 8)figure Scheme 7
Figure 8(p. 9)figure Figure 8
Table 4(p. 9)table Table 4

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon dioxide
catalyst design
CO2 hydrogenation
CO2 reduction
formic acid
hydricity
transition-metal hydride