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Special Issue "Group 11 Metal Complexes with N-Heterocyclic Carbene Ligands: Recent Developments"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (30 June 2017).

Special Issue Information

Dear Colleagues,

The major role of N-heterocyclic carbene (NHCs) as an essential class of ligands in organometallic chemistry is now well-established. The corresponding metal–NHC complexes have been extensively investigated for catalytic applications with a wide range of metals. Furthermore, some metal–NHC complexes have been shown to present interesting properties for medicinal applications. NHCs are also highly promising ligands for the development of functionalized metal-based materials. They have been involved as free NHCs or in metal–NHC complexes for the preparation/stabilization of metal-based nanoparticles and self-assembled monolayers (SAMs). Metal–NHC complexes with group 11 metals hold an important place in these different research areas and present a significant potential for future applications.

This Special Issue of Molecules will seek to highlight recent developments of metal–NHC complexes with group 11 metals (metal = Cu, Ag, Au) in a range of areas including the preparation and structure of Cu, Ag or Au–NHC complexes, catalysis, biological applications, nanomaterials and surfaces, and supramolecular chemistry.

Dr. Sylvain Roland
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • N-Heterocyclic carbenes
  • Group 11 metals
  • Coordination chemistry
  • Catalysis
  • Bioorganometallic chemistry
  • Nanomaterials and surfaces
  • Supramolecular chemistry

Published Papers (3 papers)

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Research

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Open AccessArticle
N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3] and [Ge9RI2]2 with R = Si(iPr)3 and RI = Si(TMS)3
Molecules 2017, 22(7), 1204; https://doi.org/10.3390/molecules22071204 - 19 Jul 2017
Cited by 14
Abstract
We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene) compounds of the germanium-rich metalloid clusters [Ge9R3] and [Ge9RI2]2 with R = Si(iPr)3 and [...] Read more.
We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene) compounds of the germanium-rich metalloid clusters [Ge9R3] and [Ge9RI2]2 with R = Si(iPr)3 and RI = Si(TMS)3. NHCDippCu{η3Ge9R3} with R = Si(iPr)3 (1) represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(iBu)3 or Si(TMS)3. The coordination of the [NHCDippCu]+ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge9] cluster. Furthermore, a series of novel Zintl cluster coinage metal NHC compounds of the type (NHCM)23Ge9RI2} (RI = Si(TMS)3 M = Cu, Ag and Au; NHC = NHCDipp or NHCMes) is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12Ge17 with Si(TMS)3Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au), or via a homogenous reaction using the preformed bis-silylated cluster K2[Ge9(Si(TMS)3)2] and the corresponding NHCMCl (M = Cu, Ag, Au) complex. The molecular structures of NHCDippCu{η3Ge9(Si(iPr)3)3} (1) and (NHCDippCu)23-Ge9(Si(TMS)3)2} (2) were determined by single crystal X-ray diffraction methods. In 2, the coordination of the [NHCDippCu]+ moieties to the cluster unit takes place via both open triangular faces of the [Ge9] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (1H, 13C, 29Si) and ESI-MS. Full article
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Open AccessArticle
Coinage Metal Complexes of the Carbenic Tautomer of a Conjugated Mesomeric Betaine Akin to Nitron
Molecules 2017, 22(7), 1133; https://doi.org/10.3390/molecules22071133 - 07 Jul 2017
Cited by 3
Abstract
This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an [...] Read more.
This study was motivated by our recent observation that the analytical reagent Nitron (2) is an “instant carbene”, whose reaction with coinage metal salts MX afforded complexes of its carbenic tautomer 1,4-diphenyl-3-phenylamino-1,2,4-triazol-5-ylidene (2′). Our aim was to establish an alkyl homologue of 2 in order to achieve a carbenic tautomer of higher donicity. For this purpose 1-tert-butyl-4-methyl-1,2,4-triazol-4-ium-3-tert-butylaminide (6) was synthesized. Its reactions with MX afforded complexes of the carbenic tautomer 1-tert-butyl-3-tert-butylamino-4-methyl-1,2,4-triazol-5-ylidene (6′). With a stoichiometric ratio of 1:1 complexes of the type [MX(6′)] were obtained. A ratio of 2:1 furnished complexes of the type [MX(6′)2] or [M(6′)2]X. 6′ is a better σ-donor and less electrophilic than 2′ according to NMR spectroscopic data of 6H[BF4] and 6′ = Se, respectively, and IR spectroscopic data of [RhCl(6′)(CO)2] confirm that its net electron donor capacity is superior to that of 2′. A comparison of the complexes of 2′ and 6′ reveals two pronounced structural differences. [CuX(6′)2] (X = Cl, Br) exhibit more acute C‒Cu‒C bond angles than [CuX(2′)2]. In contrast to [CuCl(2′)], [CuCl(6′)] aggregates through Cu···Cu contacts of ca. 2.87 Å, compatible with cuprophilic interactions. These differences may be explained by the complementary steric requirements of the t-Bu and the Me substituent of 6′. Full article
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Review

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Open AccessReview
Recent Developments in the Medicinal Applications of Silver-NHC Complexes and Imidazolium Salts
Molecules 2017, 22(8), 1263; https://doi.org/10.3390/molecules22081263 - 27 Jul 2017
Cited by 29
Abstract
Because of their great structural diversity and multitude of chemical properties, N-heterocyclic carbenes (NHCs) have been utilized in a variety of capacities. Most recently, NHCs have been utilized as carrier molecules for many transition metals in medicinal chemistry. Specifically, Ag(I)-NHCs have been investigated [...] Read more.
Because of their great structural diversity and multitude of chemical properties, N-heterocyclic carbenes (NHCs) have been utilized in a variety of capacities. Most recently, NHCs have been utilized as carrier molecules for many transition metals in medicinal chemistry. Specifically, Ag(I)-NHCs have been investigated as potent antibacterial agents and chemotherapeutics and have shown great efficacy in both in vitro and in vivo studies. Ag(I)-NHC compounds have been shown to be effective against a wide range of both Gram-positive and Gram-negative bacterial strains. Many compounds have also shown great efficacy as antitumor agents demonstrating comparable or better antitumor activity than standard chemotherapeutics such as cisplatin and 5-fluorouracil. While these compounds have shown great promise, clinical use has remained an unattained goal. Current research has been focused upon synthesis of novel Ag(I)-NHC compounds and further investigations of their antibacterial and antitumor activity. This review will focus on recent advances of Ag(I)-NHCs in medicinal applications. Full article
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