Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel
Abstract
The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consist ently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favour able in others. The hydricity of a water-soluble, bis-phosphine nickel hydride complex was compared to the hydricity of formate in water and in acetonitrile. Formate is a better hydride donor than [HNi(dmpe)2]+ by 7 kcal mol-1 in acetonitrile, and no hydride transfer from [HNi(dmpe)2]+ to CO2 occurs in this solvent. The hydricity of [HNi(dmpe)2]+ is greatly improved in water relative to acetonitrile, in that reduction of CO2 to formate by [HNi(dmpe)2]+ was found to be thermodynamically downhill by 8 kcal mol-1. Catalysis for the hydrogenation of CO2 was pursued; however, the regeneration of [HNi(dmpe)2] under catalytic conditions was unfavourable. However, the present results demonstrate that the solvent dependence of thermodynamic parameters such as hydricity and acidity can be exploited in order to produce systems with balanced or favourable overall thermodynamics. This approach should be advantageous for the designmore »
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1842988
- Report Number(s):
- PNNL-SA-111204
Journal ID: ISSN 1477-9226
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 45; Journal Issue: 24; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Connelly-Robinson, Samantha J., Zall, Christopher M., Miller, Deanna L., Linehan, John C., and Appel, Aaron M. Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel. United States: N. p., 2016.
Web. doi:10.1039/c6dt00309e.
Connelly-Robinson, Samantha J., Zall, Christopher M., Miller, Deanna L., Linehan, John C., & Appel, Aaron M. Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel. United States. https://doi.org/10.1039/c6dt00309e
Connelly-Robinson, Samantha J., Zall, Christopher M., Miller, Deanna L., Linehan, John C., and Appel, Aaron M. Tue .
"Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel". United States. https://doi.org/10.1039/c6dt00309e. https://www.osti.gov/servlets/purl/1842988.
@article{osti_1842988,
title = {Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel},
author = {Connelly-Robinson, Samantha J. and Zall, Christopher M. and Miller, Deanna L. and Linehan, John C. and Appel, Aaron M.},
abstractNote = {The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consist ently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favour able in others. The hydricity of a water-soluble, bis-phosphine nickel hydride complex was compared to the hydricity of formate in water and in acetonitrile. Formate is a better hydride donor than [HNi(dmpe)2]+ by 7 kcal mol-1 in acetonitrile, and no hydride transfer from [HNi(dmpe)2]+ to CO2 occurs in this solvent. The hydricity of [HNi(dmpe)2]+ is greatly improved in water relative to acetonitrile, in that reduction of CO2 to formate by [HNi(dmpe)2]+ was found to be thermodynamically downhill by 8 kcal mol-1. Catalysis for the hydrogenation of CO2 was pursued; however, the regeneration of [HNi(dmpe)2] under catalytic conditions was unfavourable. However, the present results demonstrate that the solvent dependence of thermodynamic parameters such as hydricity and acidity can be exploited in order to produce systems with balanced or favourable overall thermodynamics. This approach should be advantageous for the design of future water-soluble catalysts.},
doi = {10.1039/c6dt00309e},
journal = {Dalton Transactions},
number = 24,
volume = 45,
place = {United States},
year = {Tue Apr 12 00:00:00 EDT 2016},
month = {Tue Apr 12 00:00:00 EDT 2016}
}
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