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Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn3 and HgZn2 Metal Clusters.

ABSTRACT: The impact of substituting Hg(II) for Zn(II) in a thiolate-bridged trinuclear cluster with parallels to a metallothionein metal cluster was investigated. A new solvomorph of [Zn(ZnL)2](ClO4)2 (1) (L = N-(2-pyridylmethyl)-N-(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(ZnL)2](ClO4)2 (2) were characterized by single-crystal X-ray crystallography. The interplay of hydrogen bonding and aromatic-packing interactions in producing lamellar, 2D lamellar, and columnar arrangements of complex cations in the crystalline state is discussed. Both variable temperature proton nuclear magnetic resonance and electrospray ion-mass spectrometry (ESI-MS) suggest that the complex ions of 1 and 2 are the predominant solution species at moderate concentrations. ESI-MS was also used to monitor differences in metal ion redistribution as 1 was titrated with Hg(ClO4)2 and [HgL(ClO4)]. These studies document the facile replacement of Zn(II) by Hg(II) with the preservation of the overall structure in thiolate-rich clusters.

SUBMITTER: Hallinger MR 

PROVIDER: S-EPMC6645076 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

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Metal Substitution and Solvomorphism in Alkylthiolate-Bridged Zn<sub>3</sub> and HgZn<sub>2</sub> Metal Clusters.

Hallinger Madeline R MR   Gerhard Alison C AC   Ritz Mikhaila D MD   Sacks Joshua S JS   Poutsma John C JC   Pike Robert D RD   Wojtas Lukasz L   Bebout Deborah C DC  

ACS omega 20171005 10

The impact of substituting Hg(II) for Zn(II) in a thiolate-bridged trinuclear cluster with parallels to a metallothionein metal cluster was investigated. A new solvomorph of [Zn(Zn<b>L</b>)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> (<b>1</b>) (<b>L</b> = <i>N</i>-(2-pyridylmethyl)-<i>N</i>-(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(Zn<b>L</b>)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub> (<b>2</b>) were characterized by single-crystal X-ray crystallography. The interplay o  ...[more]

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