Abstract
A range of modern density functional theory (DFT) functionals have been benchmarked against experimentally determined metal hydride bond strengths for three first-row TM hydride complexes. Geometries were found to be produced sufficiently accurately with RI-BP86-D3(PCM)/def2-SVP and further single-point calculations with PBE0-D3(PCM)/def2-TZVP were found to reproduce the experimental hydricity accurately, with a mean absolute deviation of 1.4 kcal/mol for the complexes studied.
Highlights
For investigation in the field of homogeneous catalysis, especially in hydrogenation reactions as shown in Scheme 1, the metal hydride bond will be of prime importance for the catalytic activity, and the functional used must be accurate in the description of these bond strengths
The explicit treatment of a solvent molecule is required to describe the role as a ligand in the coordination sphere and as such, the reaction shown in Equation (2) may be better represented by the reaction in Equation (5), where both cations are solvated by explicit solvent molecules
If a solvent molecule is coordinated to the metal centre after hydride dissociation, according to Equation (1), this binding energy is implicitly included in the experimental determination of thermodynamic hydricity by Wiedner et al [39] (Equation (2))
Summary
The metals themselves are toxic, which may lead to issues of contamination in extraction, chemical transformations, or in the application of these catalysts in industrial processes. To alleviate these issues, development has moved towards the use of 3d TMs, which are largely more abundant, less toxic and more sustainable [2,3,4,5]. For investigation in the field of homogeneous catalysis, especially in hydrogenation reactions as shown in Scheme 1, the metal hydride bond will be of prime importance for the catalytic activity, and the functional used must be accurate in the description of these bond strengths.
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Free) 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
