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

Abstract

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. J = 1-0 transitions of para-H(2)-CuF, ortho-D(2)-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% SF(6) and 3% H(2) 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.

A monomeric complex of ammonia and cuprous chloride: H3N⋯CuCl isolated and characterised by rotational spectroscopy and ab initio calculations

“…The present work exploits the cold environment generated within a gas sample undergoing supersonic expansion to produce and isolate the H 3 N• • •CuCl monomer for study. It is informed by recent experiments which have succeeded in generating a wide variety of complexes that contain metal halides coordinated to simple Lewis bases such as N 2 , 7 H 2 , 8,9 CO, [10][11][12][13][14][15] H 2 O, [16][17][18] NH 3 , 19 H 2 S, 17,20,21 C 2 H 4 , 22,23 and C 2 H 2 . 22,24 Most pertinently, the spectra of five isotopologues of H 3 N• • • AgCl were characterised and analysed to reveal aspects of the molecular geometry.…”

The covalent interaction between dihydrogen and gold: A rotational spectroscopic study of H2–AuCl

“…The subtleties of the design are given in the work of Hight Walker et al 32 and the instrument modeled after the design of the National Institute of Standards and Technology pulsed-jet FTMW spectrometer. 33 The spectrometer is equipped with a laser ablation source, 34 utilizing the fundamental of a Nd:YAG laser at 1064 nm. A gold-tipped aluminum rod was used as the source of gold for the laser ablation technique.…”

“…This structure is consistent with those observed in previous metal halide hydrogen complexes. 30,34 The binding energy D e was calculated to be 164 kJ/mol. There is also a predicted elongation of the H 2 bond upon formation of the complex from 0.795 Å in free H 2 40 to an r e value of 0.91 Å.…”

Photoelectron spectroscopic and computational study of the PtMgH3,5− cluster anions

“…† The charge distribution on each atom in both cluster anions was obtained from natural population analysis, and these are marked in blue in Fig. 3 33,34 In each of these cases, H 2 was bound to the rest of the molecule or cluster by a significant binding energy. Fig.…”