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This content will become publicly available on March 15, 2019

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