Inorganics

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Open AccessArticle

Disulfide Competition for Phosphine Gold(I) Thiolates: Phosphine Oxide Formation vs. Thiolate Disulfide Exchange

by Gamage S. P. Garusinghe, S. Max Bessey, Mostapha Aghamoosa, Meaghan McKinnon, Alice E. Bruce and Mitchell R. M. Bruce

Inorganics 2015, 3(1), 40-54; https://doi.org/10.3390/inorganics3010040 - 27 Feb 2015

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Abstract

Phosphine gold(I) thiolate complexes react with aromatic disulfides via two pathways: either thiolate–disulfide exchange or a pathway that leads to formation of phosphine oxide. We have been investigating the mechanism of gold(I) thiolate–disulfide exchange. Since the formation of phosphine oxide is a competing reaction, it is important for our kinetic analysis to understand the conditions under which phosphine oxide forms. ¹H and ³¹P{¹H} NMR, and GC-MS techniques were employed to study the mechanism of formation of phosphine oxide in reactions of R₃PAu(SRʹ) (R = Ph, Et; SRʹ = SC₆H₄CH₃, SC₆H₄Cl, SC₆H₄NO₂, or tetraacetylthioglucose (TATG)) and R*SSR* (SR* = SC₆H₄CH₃, SC₆H₄Cl, SC₆H₄NO₂, or SC₆H₃(COOH)(NO₂)). The phosphine oxide pathway is most significant for disulfides with strongly electron withdrawing groups and in high dielectric solvents, such as DMSO. Data suggest that phosphine does not dissociate from gold(I) prior to reaction with disulfide. 2D (¹H-¹H) NMR ROESY experiments are consistent with an intermediate in which the disulfide and phosphine gold(I) thiolate are in close proximity. Water is necessary but not sufficient for formation of phosphine oxide since no phosphine oxide forms in acetonitrile, a solvent, which frequently contains water. Full article

(This article belongs to the Special Issue Frontiers in Gold Chemistry)

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3239 KiB

Open AccessArticle

[AuHg(o-C₆H₄PPh₂)₂I]: A Dinuclear Heterometallic Blue Emitter

by José M. López-de-Luzuriaga, Miguel Monge, M. Elena Olmos and David Pascual

Inorganics 2015, 3(1), 27-39; https://doi.org/10.3390/inorganics3010027 - 11 Feb 2015

Cited by 9 | Viewed by 6218

Abstract

The heteronuclear Au^I/Hg^II complex [AuHg(o-C₆H₄PPh₂)₂I] (1) was prepared by reacting of [Hg(2-C₆H₄PPh₂)₂] with [Au(tht)₂]ClO₄ (1:1) and NaI [...] Read more.

The heteronuclear Au^I/Hg^II complex [AuHg(o-C₆H₄PPh₂)₂I] (1) was prepared by reacting of [Hg(2-C₆H₄PPh₂)₂] with [Au(tht)₂]ClO₄ (1:1) and NaI in excess. The heterometallic compound 1 has been structurally characterized and shows an unusual blue luminescent emission in the solid state. Theoretical calculations suggest that that the origin of the emission arises from the iodide ligand arriving at metal-based orbitals in a Ligand to Metal-Metal Charge Transfer transition. Full article

(This article belongs to the Special Issue Frontiers in Gold Chemistry)

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1697 KiB

Open AccessCommunication

A New Nanometer-Sized Ga(III)-Oxyhydroxide Cation

by William H. Casey, Marilyn M. Olmstead, Caitlyn R. Hazlett, Chelsey Lamar and Tori Z. Forbes

Inorganics 2015, 3(1), 21-26; https://doi.org/10.3390/inorganics3010021 - 3 Feb 2015

Cited by 6 | Viewed by 6384

Abstract

A new 30-center Ga(III)-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl₃ solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS). The cluster has 30 metal centers and a nominal stoichiometry: [Ga₃₀(μ₄-O)₁₂(μ₃-O)₄(μ₃-OH)₄(μ₂-OH)₄₂(H₂O)₁₆](2,6-NDS)₆, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III) cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O)₄ centers and sets of both protonated and unprotonated μ₃-oxo. Full article

(This article belongs to the Special Issue Polyoxometalates)

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141 KiB

Open AccessEditorial

Acknowledgement to Reviewers of Inorganics in 2014

by Inorganics Editorial Office

Inorganics 2015, 3(1), 19-20; https://doi.org/10.3390/inorganics3010019 - 8 Jan 2015

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Abstract

The editors of Inorganics would like to express their sincere gratitude to the following reviewers for assessing manuscripts in 2014:[...] Full article

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Open AccessReview

Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

by João Carlos Lima and Laura Rodríguez

Inorganics 2015, 3(1), 1-18; https://doi.org/10.3390/inorganics3010001 - 31 Dec 2014

Cited by 46 | Viewed by 9053

Abstract

Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators). A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I) complexes. There are also some Au(III) derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies. Full article

(This article belongs to the Special Issue Frontiers in Gold Chemistry)

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Inorganics, Volume 3, Issue 1 (March 2015) – 5 articles , Pages 1-54

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