Thermodynamic and kinetic hydricities of metal-free hydrides

Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B.; Glusac, Ksenija D.

doi:10.1039/C7CS00171A

Title: Thermodynamic and kinetic hydricities of metal-free hydrides

Journal Article · Thu Mar 15 00:00:00 EDT 2018 · Chemical Society Reviews

DOI:https://doi.org/10.1039/C7CS00171A· OSTI ID:1467650

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Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Colorado, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

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 (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 CO₂ reduction and hydrogen activation with frustrated Lewis pairs.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Petroleum Research Fund (PRF); National Science Foundation (NSF); Ohio Supercomputer Center (OSC); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1467650

Journal Information:: Chemical Society Reviews, Vol. 47, Issue 8; ISSN 0306-0012

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 82 works

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