Role of Dispersion in Metallophilic Hg···M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yl)mercury

Emanuel Hupf; Ralf Kather; Matthias Vogt; Enno Lork; Stefan Mebs; Jens Beckmann

doi:10.1021/acs.inorgchem.6b02056

Role of Dispersion in Metallophilic Hg···M Interactions (M = Cu, Ag, Au) within Coinage Metal Complexes of Bis(6-diphenylphosphinoacenaphth-5-yl)mercury

Inorg Chem. 2016 Nov 7;55(21):11513-11521. doi: 10.1021/acs.inorgchem.6b02056. Epub 2016 Oct 17.

Authors

Emanuel Hupf¹, Ralf Kather¹, Matthias Vogt¹, Enno Lork¹, Stefan Mebs², Jens Beckmann¹

Affiliations

¹ Institut für Anorganische Chemie und Kristallographie, Universität Bremen , Leobener Strasse, 28359 Bremen, Germany.
² Institut für Experimentalphysik, Freie Universität Berlin , Arnimallee 14, 14195 Berlin, Germany.

PMID: 27749049
DOI: 10.1021/acs.inorgchem.6b02056

Abstract

The previously reported bis(6-diphenylphosphinoacenaphth-5-yl)mercury (1) was used as ligand for the preparation of the copper(I) complexes, 1·CuCl and [1·Cu(NCMe)]BF₄, which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations employing topological analysis of the electron and electron pair densities within the AIM and ELI-D space-partitioning schemes revealed significant metallophilic Hg···Cu interactions. Evaluation of noncovalent bonding aspects according to the noncovalent interaction (NCI) index was applied not only for the Cu complexes 1·CuCl and [1·Cu(NCMe)]BF₄ but also for the previously reported Ag and Au complexes, namely, [1·MCl] (M = Ag, Au) and [1·M(NCMe)_n]⁺ (M = Ag, n = 2; M = Au, n = 0), and facilitated the assignment of attractive dispersive Hg···M interactions with the Hg···Cu contacts being comparable to the Hg···Ag but weaker than the Hg···Au interactions. The localization of the attractive noncovalent bonding regions increases in the order Cu < Ag < Au.