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Issue 26, 2020
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Metallophilic interactions: observations of the shortest metallophilicinteractions between closed shell (d10⋯d10, d10⋯d8, d8⋯d8) metal ions [M⋯M′ M = Hg(ii) and Pd(ii) and M′ = Cu(i), Ag(i), Au(i), and Pd(ii)]

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Abstract

The salt metathesis reaction of two equivalents of 8-lithioquinoline (C6H6NLi) with HgBr2 afforded bis(quinoline-8-yl)mercury, [(C6H6N)2Hg]. Bis(quinoline-8-yl)mercury has been used for the synthesis of a series of heteronuclear complexes of the type [(C6H6N)2M·M′]·Xn [M = Hg; {M′ = Cu, X = ClO4; X = I; X = CF3SO3}, {M′ = Ag, X = ClO4; X = CF3SO3; X = BF4}, {M′ = Au, X = CF3SO3}; {M′ = Pd, X = CF3CO2}], [M = Pd; M′ = Pd, X = CF3CO2; n = 2]. All the complexes were well characterized by multinuclear NMR (1H, 13C, 19F, 11B, 199Hg) spectroscopic analysis. Their structures were determined by single crystal X-ray diffraction studies, which displayed the shortest Hg⋯M′ (M′ = Cu, Ag, Au, Pd) metallophilic interactions. The electronic properties of the molecular structures were determined by DFT calculations. ELF (Electron Localization Function) analysis provided the information about the localization of electrons between metal⋯metal bonds and dispersion of electron density around the metal ions. The AIM (Atoms in Molecule) analysis revealed the presence of electron density at the bond critical points (bcp) and the strengths of M⋯M′ [M = Hg, M′ = Cu, Ag, Au, Pd; M, M′=Pd] interactions. The NBO (Natural Bond Orbital) analysis was used to identify the donor–acceptor character of the orbitals involved in the bonding.

Graphical abstract: Metallophilic interactions: observations of the shortest metallophilicinteractions between closed shell (d10⋯d10, d10⋯d8, d8⋯d8) metal ions [M⋯M′ M = Hg(ii) and Pd(ii) and M′ = Cu(i), Ag(i), Au(i), and Pd(ii)]

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Supplementary files

Article information


Submitted
17 Mar 2020
Accepted
03 Jun 2020
First published
05 Jun 2020

Dalton Trans., 2020,49, 9099-9117
Article type
Paper

Metallophilic interactions: observations of the shortest metallophilicinteractions between closed shell (d10⋯d10, d10⋯d8, d8⋯d8) metal ions [M⋯M′ M = Hg(II) and Pd(II) and M′ = Cu(I), Ag(I), Au(I), and Pd(II)]

S. Raju, H. B. Singh and R. J. Butcher, Dalton Trans., 2020, 49, 9099
DOI: 10.1039/D0DT01008A

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