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Title: Thermodynamic and kinetic hydricities of metal-free hydrides

Metal-free hydrides are of increasing research interest due to their roles in recent scientific advances in catalysis, such as hydrogen activation with frustrated Lewis pairs and electrocatalytic CO 2 reduction with pyridinium and other aromatic cations. The structural design of hydrides for specific applications necessitates the correct description of their thermodynamic and kinetic prowess using reliable parameters – thermodynamic hydricity (ΔG H) and nucleophilicity ( N). This review summarizes reported experimental and calculated hydricity values for more than 200 metal-free hydride donors, including carbon-, boron-, nitrogen- and silicon-based hydrides. We describe different experimental and computational methods used to obtain these thermodynamic and kinetic parameters. Furthermore, tabulated data on metal-free hydrides are discussed in terms of structure–property relationships, relevance to catalysis and contemporary limitations for replacing transition-metal hydride catalysts. Lastly, several selected applications of metal-free hydrides in catalysis are described, including photosynthetic CO 2 reduction and hydrogen activation with frustrated Lewis pairs.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of Colorado, Boulder, CO (United States)
  3. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Chemical Society Reviews
Additional Journal Information:
Journal Volume: 47; Journal Issue: 8; Journal ID: ISSN 0306-0012
Publisher:
Royal Society of Chemistry
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
Petroleum Research Fund (PRF); National Science Foundation (NSF); Ohio Supercomputer Center (OSC); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1467650

Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., and Glusac, Ksenija D.. Thermodynamic and kinetic hydricities of metal-free hydrides. United States: N. p., Web. doi:10.1039/C7CS00171A.
Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., & Glusac, Ksenija D.. Thermodynamic and kinetic hydricities of metal-free hydrides. United States. doi:10.1039/C7CS00171A.
Ilic, Stefan, Alherz, Abdulaziz, Musgrave, Charles B., and Glusac, Ksenija D.. 2018. "Thermodynamic and kinetic hydricities of metal-free hydrides". United States. doi:10.1039/C7CS00171A.
@article{osti_1467650,
title = {Thermodynamic and kinetic hydricities of metal-free hydrides},
author = {Ilic, Stefan and Alherz, Abdulaziz and Musgrave, Charles B. and Glusac, Ksenija D.},
abstractNote = {Metal-free hydrides are of increasing research interest due to their roles in recent scientific advances in catalysis, such as hydrogen activation with frustrated Lewis pairs and electrocatalytic CO2 reduction with pyridinium and other aromatic cations. The structural design of hydrides for specific applications necessitates the correct description of their thermodynamic and kinetic prowess using reliable parameters – thermodynamic hydricity (ΔGH–) and nucleophilicity (N). This review summarizes reported experimental and calculated hydricity values for more than 200 metal-free hydride donors, including carbon-, boron-, nitrogen- and silicon-based hydrides. We describe different experimental and computational methods used to obtain these thermodynamic and kinetic parameters. Furthermore, tabulated data on metal-free hydrides are discussed in terms of structure–property relationships, relevance to catalysis and contemporary limitations for replacing transition-metal hydride catalysts. Lastly, several selected applications of metal-free hydrides in catalysis are described, including photosynthetic CO2 reduction and hydrogen activation with frustrated Lewis pairs.},
doi = {10.1039/C7CS00171A},
journal = {Chemical Society Reviews},
number = 8,
volume = 47,
place = {United States},
year = {2018},
month = {3}
}

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