Thermodynamic and kinetic hydricities of metal-free hydrides

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

doi:10.1039/C7CS00171A

Thermodynamic and kinetic hydricities of metal-free hydrides

Chem Soc Rev. 2018 Apr 23;47(8):2809-2836. doi: 10.1039/C7CS00171A.

Authors

Stefan Ilic¹, Abdulaziz Alherz², Charles B Musgrave³, Ksenija D Glusac¹

Affiliations

¹ Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607, USA. glusac@uic.edu and Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA.
² Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO 80309, USA.
³ Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO 80309, USA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA and Materials and Chemical Science and Technology Center, National Renewable Energy Laboratory, Golden, CO 80401, USA.

PMID: 29543931
DOI: 10.1039/C7CS00171A

Abstract

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. Finally, several selected applications of metal-free hydrides in catalysis are described, including photosynthetic CO2 reduction and hydrogen activation with frustrated Lewis pairs.

Publication types

Review