Issue 12, 2016

Supramolecular aggregation of Ni(salen) with (C6F5)2Hg and [o-C6F4Hg]3

Abstract

As part of our ongoing interest in the supramolecular chemistry of fluorinated organomercurials, we have investigated the interaction of bis(pentafluorophenyl)mercury ((C6F5)2Hg), and trimeric (perfluoro-o-phenylene)mercury ([o-C6F4Hg]3), with nickel(II) N,N′-bis(salicylidene)ethylenediamine) (Ni(salen)). While solution studies monitored by UV-VIS spectroscopy suggest that Ni(salen) interacts with the trinuclear mercury complex in solution, the 1 : 1 adduct (Ni(salen)-(C6F5)2Hg) and the 1 : 1 adducts Ni(salen)-[o-C6F4Hg]3 and [Ni(salen)-[o-C6F4Hg]3-THF-H2O] can be obtained by slow evaporation of solutions containing the two building blocks. While arene–fluoroarene and hydrogen bonding interactions, as well as interactions between mercury and the salen ligand are the predominant forces responsible for the formation of these adducts, Ni(salen)-[o-C6F4Hg]3 and [Ni(salen)-[o-C6F4Hg]3-THF-H2O] also display short Ni–Hg separations consistent with the presence of metallophilic interactions. Quantum theory of atoms in molecules (QTAIM) analyses of the Ni–Hg interactions in these adducts finds that these interactions are dominated by electrostatic and dispersion forces, despite featuring non-negligible covalent contributions.

Graphical abstract: Supramolecular aggregation of Ni(salen) with (C6F5)2Hg and [o-C6F4Hg]3

Supplementary files

Article information

Article type
Paper
Submitted
19 Maijs 2015
Accepted
03 Febr. 2016
First published
04 Febr. 2016

Dalton Trans., 2016,45, 5045-5051

Supramolecular aggregation of Ni(salen) with (C6F5)2Hg and [o-C6F4Hg]3

M. Tsunoda, M. Fleischmann, J. S. Jones, N. Bhuvanesh, M. Scheer and F. P. Gabbaï, Dalton Trans., 2016, 45, 5045 DOI: 10.1039/C5DT01887K

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