Probing the Chemical Nature of Dihydrogen Complexation to Transition Metals, a Gas Phase Case Study: H₂–CuF

This work details a gas phase study of the bonding of hydrogen to the metal in a simple diatomic analogue of a metal organic framework (MOF), copper fluoride, via dihydrogen complexation. This is the first microwave study of these types of interactions. <i>J</i> = 1–0 transitions of <i>para</i>-H₂–CuF, <i>ortho</i>-D₂–CuF, and HD–CuF have been measured and analyzed. The complexes were prepared by laser ablating a metal copper rod in the presence of a gas mix of 0.6% SF₆ and 3% H₂ in Ar undergoing supersonic expansion. The binding energy of this complex is addressed through quantum chemical calculations and measured nuclear quadrupole coupling constants for copper and deuterium. The significant change in the calculated binding energy and nuclear quadrupole coupling constants in relation to similar molecules suggest bonding greater than that typical of van der Waals interactions