Thermodynamic and kinetic studies of H₂ and N₂ binding to bimetallic nickel-group 13 complexes and neutron structure of a Ni(η²-H₂) adduct

Abstract

Binding energies for H2 and N2 at nickel become more exergonic for the larger group 13 sigma-accepting supports.

Computational Study of Triphosphine-Ligated Cu(I) Catalysts for Hydrogenation of CO2 to Formate

“…Since the d-shell of a Cu + ion is filled, at low energy, and contracted, little backbonding and a weak Cu–H 2 interaction are to be expected. Notably, the majority of stable M–H 2 complexes contain d 6 metal centers, whereas d 8 dihydrogen complexes are uncommon and reactive, and first-row d 10 dihydrogen complexes are even more rare; known complexes include Lewis acidic atoms, such as boron − and heavier group 13 metals, − bound to the metal. The H 2 –CuF complex has been studied in the gas phase by microwave spectroscopy and at the DFT/APF-D plus a large basis set level; the binding mode is side-on, and the primary-bonding interactions were found to be σ-donation from H 2 to a Cu orbital with primarily 4s character and a backbonding interaction with a Cu d orbital; thus, electron density was transferred from H 2 to the CuF unit, decreasing the charge on Cu by greater than 0.1.…”

“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.1c04050. Complete citations for refs , and ; tables of calculated reaction free energies in the gas phase and acetonitrile with B3LYP, PW91, M06, and ωB97XD functionals; tables of relative free energies in the gas phase and acetonitrile for listed functionals; additional figures of the reaction coordinate study of H 2 splitting; table of charges; MO plots and energies; natural population analysis charges and NBO analysis; and optimized Cartesian coordinates (PDF) …”

Sulfonium cations as versatile strongly π-acidic ligands

“…For instance, extending the chemistry of B, Al, Ga, Sn, and Bi gave birth to the concept of σ-acceptor (aka Z-type) ligands. 1 Peters, 2 Lu 3 and others 4 have used complexes of these ligands for such fundamentally important processes as N 2 fixation, CO 2 reduction, and H 2 activation.…”

The H•/H– Redox Couple and Absolute Hydration Energy of H–

“…Hydration of ions plays a vital role in aqueous chemical and biological systems. − The solvation of the H – (hydride) anion is important in developing an absolute hydricity scale for designing catalytic processes, especially those involving hydride transfer. − The gas-phase fluoride and hydride affinity scales have been used to predict Lewis acidities and associated reactivity patterns, , following the gas-phase proton affinity scale that has been broadly developed and applied. It was possible using a range of techniques to get an absolute proton affinity scale, although much of the initial proton affinity scale was developed as sets of relative scales.…”