Frontiers in Gold Chemistry

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (15 October 2014) | Viewed by 54129

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Guest Editor
Department of Chemistry, Delaware State University, 1200 N DuPont Highway, Dover, DE 19901, USA
Interests: synthesis of gold complexes; optical properties of gold complexes; gold-carbon nanoparticles and thin films; mechanism of gold catalysis; antifouling properties of gold-carbon nanoparticles and gold thiolate complexes in rheumatoid arthritis treatment

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Guest Editor
Departamento de Quimica Inorganica, ICMA, Universidad de Zaragoza-CSIC, Pedro Cerbuna 12, 50009-Zaragoza, Spain
Interests: synthesis and characterization of gold and silver complexes; structural, optical and medical properties of gold and silver derivatives, cyclo- and polyhosphazene derivatives; coordination chemistry of group 11 elements

Special Issue Information

Dear Colleagues,

The chemistry of the Sleeping Beauty gold has attracted interest in basic chemistry and applications. Why is gold so attractive? Gold complexes have shown applications in volatile organic compound sensors, liquid crystal displays, optical limiting diodes, surface modification, and rheumatoid arthritis treatment. Gold has served as the main initiative in nanotechnology applications in catalysis, cancer detection, and energy conversion. Aurophilic bonding, which reproduces the attractive forces between the gold atoms, has imparted unique properties in gold chemistry and probably is the foundation of the unique electronic and optoelectronic properties of gold. This Special Issue focuses on recent advances in gold chemistry toward synthesis and applications in the optical, medical, nanotechnological, and catalytic fields.

Dr. Ahmed A. Mohamed
Prof. Dr. Antonio Laguna
Guest Editors

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Keywords

  • Synthesis of gold complexes
  • gold nanoparticles;
  • optical properties of gold complexes;
  • theoretical calculations involving gold;
  • medical applications of gold;
  • materials chemistry of gold;
  • catalysis using gold

Published Papers (9 papers)

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Editorial

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631 KiB  
Editorial
Frontiers in Gold Chemistry
by Ahmed A. Mohamed
Inorganics 2015, 3(3), 370-373; https://doi.org/10.3390/inorganics3030370 - 24 Aug 2015
Cited by 1 | Viewed by 3433
Abstract
Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry [...] Read more.
Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of gold. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)

Research

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1731 KiB  
Article
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
Cited by 6 | Viewed by 7525
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 [...] Read more.
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  
Article
[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 5848
Abstract
The heteronuclear AuI/HgII 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 AuI/HgII 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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756 KiB  
Article
Various Oxygen-Centered Phosphanegold(I) Cluster Cations Formed by Polyoxometalate (POM)-Mediated Clusterization: Effects of POMs and Phosphanes
by Takuya Yoshida, Yuta Yasuda, Eri Nagashima, Hidekazu Arai, Satoshi Matsunaga and Kenji Nomiya
Inorganics 2014, 2(4), 660-673; https://doi.org/10.3390/inorganics2040660 - 10 Dec 2014
Cited by 14 | Viewed by 5261
Abstract
Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})44-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m [...] Read more.
Novel phosphanegold(I) cluster cations combined with polyoxometalate (POM) anions, i.e., intercluster compounds, [(Au{P(m-FPh)3})44-O)]2[{(Au{P(m-FPh)3})2 (μ-OH)}2][α-PMo12O40]2·EtOH (1), [(Au{P(m-FPh)3})44-O)]2[α-SiMo12O40]·4H2O (2), [(Au{P(m-MePh)3})44-O)]2[α-SiM12O40] (M = W (3), Mo (4)) and [{(Au {P(p-MePh)3})44-O)}{(Au{P(p-MePh)3})33-O)}][α-PW12O40] (5) were synthesized by POM-mediated clusterization, and unequivocally characterized by elemental analysis, TG/DTA, FT-IR, X-ray crystallography, solid-state CPMAS 31P NMR and solution (1H, 31P{1H}) NMR. Formation of the these gold(I) cluster cations was strongly dependent upon the charge density and acidity of the POMs, and the substituents and substituted positions on the aryl group of triarylphosphane ligands. These gold(I) cluster cations contained various bridged-oxygen atoms such as μ4-O, μ3-O and μ-OH groups. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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890 KiB  
Article
Reactivity of Mononuclear and Dinuclear Gold(I) Amidinate Complexes with CS2 and CsBr3
by Andrew C. Lane, Charles L. Barnes, Matthew V. Vollmer and Justin R. Walensky
Inorganics 2014, 2(4), 540-551; https://doi.org/10.3390/inorganics2040540 - 08 Oct 2014
Cited by 7 | Viewed by 5568
Abstract
To probe the reactivity of gold-nitrogen bonds, we have examined the insertion chemistry with carbon disulfide (CS2) as well as oxidation with cesium tribromide (CsBr3) with Au(I) amidinate complexes. The reaction of Ph3PAuCl with Na[(2,6-Me2C [...] Read more.
To probe the reactivity of gold-nitrogen bonds, we have examined the insertion chemistry with carbon disulfide (CS2) as well as oxidation with cesium tribromide (CsBr3) with Au(I) amidinate complexes. The reaction of Ph3PAuCl with Na[(2,6-Me2C6H3N)2C(H)] yields the mononuclear, two-coordinate gold(I) complex, Ph3PAu[κ1-(2,6-Me2C6H3N)2C(H)], 1. The reactivity of 1 with CS2 produced the mononuclear Au(I) compound, Ph3PAu{κ1-S2C[(2,6-Me2C6H3N)2C(H)]}, 2. In the case of CsBr3 the previously reported dinuclear Au(I) complex, Au[(2,6-Me2C6H3N)2C(H)]2, 3, was isolated with formation of Ph3PBr2. We also compared the reactivity of CS2 and CsBr3 with 3. Carbon disulfide insertion with 3 produces a dimeric product, Aun[CS2(2,6-Me2C6H3NC(H)=NC6H3Me2)]n, 4, featuring a dinuclear core with linking aurophilic interactions, making it appear polymeric in the solid state. When CsBr3 is reacted with 3 the Au(II,II) product is obtained, Au2[(2,6-Me2C6H3N)2C(H)]2(Br)2, 5. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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1052 KiB  
Article
Gold Thione Complexes
by Francesco Caddeo, Vanesa Fernández-Moreira, Massimiliano Arca, Antonio Laguna, Vito Lippolis and M. Concepción Gimeno
Inorganics 2014, 2(3), 424-432; https://doi.org/10.3390/inorganics2030424 - 04 Aug 2014
Cited by 6 | Viewed by 5034
Abstract
The reaction of the ligand Et4todit (4,5,6,7-Tetrathiocino-[1,2-b:3,4-b']-diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione) with gold complexes leads to the dinuclear gold(I) complexes [{Au(C6F5)}2(Et4todit)] and [Au(Et4todit)]2(OTf)2, which do not contain [...] Read more.
The reaction of the ligand Et4todit (4,5,6,7-Tetrathiocino-[1,2-b:3,4-b']-diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione) with gold complexes leads to the dinuclear gold(I) complexes [{Au(C6F5)}2(Et4todit)] and [Au(Et4todit)]2(OTf)2, which do not contain any gold-gold interactions, or to the gold(III) derivative [{Au(C6F5)3}2(Et4todit)]. The crystal structures have been established by X-ray diffraction studies and show that the gold centers coordinate to the sulfur atoms of the imidazoline-2-thione groups. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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Review

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2335 KiB  
Review
Gilded Hope for Medicine
by Mohamed El Naggar, Ihsan Shehadi, Hanan E. Abdou and Ahmed A. Mohamed
Inorganics 2015, 3(2), 139-154; https://doi.org/10.3390/inorganics3020139 - 15 May 2015
Cited by 3 | Viewed by 5981
Abstract
Gold is emerging as a potential therapeutic agent in the treatment of arthritis, cancer and AIDS. The therapeutic mechanism of arthritic gold drugs and their modification in the presence of stomach hydrochloric acid, in the joints, and in the presence of mild and [...] Read more.
Gold is emerging as a potential therapeutic agent in the treatment of arthritis, cancer and AIDS. The therapeutic mechanism of arthritic gold drugs and their modification in the presence of stomach hydrochloric acid, in the joints, and in the presence of mild and strong oxidizing agents is a matter of debate. It is believed that gold affects the entire immune response and reduces its potency and limits its oxidizing nature. DNA apparently is not the main target of gold in cancer treatment. Rheumatoid arthritis, cancer, heart diseases and recently AIDS have all been targeted with gold nanoparticles therapy. The era of gold nanoparticles started with cancer imaging and treatment studies. Gold nanoparticles have emerged as smart drug vehicles. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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1733 KiB  
Review
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 8682
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 [...] Read more.
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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1204 KiB  
Review
Gold Liquid Crystals in the XXI Century
by Manuel Bardají
Inorganics 2014, 2(3), 433-454; https://doi.org/10.3390/inorganics2030433 - 06 Aug 2014
Cited by 12 | Viewed by 6115
Abstract
Since the first gold liquid crystal was described in 1986, much effort has been done to prepare new compounds bearing this property. The review deals with the last results obtained in this new century. Gold(I) has a strong affinity to give linear co-ordination [...] Read more.
Since the first gold liquid crystal was described in 1986, much effort has been done to prepare new compounds bearing this property. The review deals with the last results obtained in this new century. Gold(I) has a strong affinity to give linear co-ordination and metal-metal interactions, which produce a rich supramolecular chemistry, and can promote the behavior as liquid crystal. Therefore, most liquid crystals are based on rod-like gold(I) compounds, while gold(III) liquid crystals are scarce. Calamitic and discotic mesogens have been reported, as well as chiral liquid crystals. Weak interactions such as H-bonds have also been used to obtain gold mesogens. Some of them exhibit additional properties, such as color, luminescence, and chirality. Luminescence has been reported, not only in the solid state or in solution, but also in the mesophase. This is relevant for applications in LEDs (Light Emitting Diodes), information storage, and sensors. Full article
(This article belongs to the Special Issue Frontiers in Gold Chemistry)
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