Submit to Catalysts Review for Catalysts Propose a Special Issue

Journal Browser

Late Transition Metal Complexes: Catalytic and/or Biological Activities

Print Special Issue Flyer
Special Issue Editors
Special Issue Information
Keywords
Published Papers

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: closed (31 August 2022) | Viewed by 15449

Share This Special Issue

Special Issue Editors

Dr. Annaluisa Mariconda

E-Mail Website
Guest Editor

Department of Science (DIS), University of Basilicata, Potenza, Italy
Interests: NHC -silver, -gold and -ruthenium complexes; A3-coupling reactions; hydroamination of alkynes; olefin metathesis reactions; polymerizations; self-healing materials; metal N-heterocyclic carbene complexes as potential antitumor
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Pasquale Longo

E-Mail Website
Guest Editor

Department of Chemistry and Biology "A. Zambelli", University of Salerno, 84084 Fisciano, Italy
Interests: organometallic chemistry; homogeneous catalysis; polymerization of olefins; organometallic complexes having antitumoral activity; self-healing materials
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Late transition metal (groups from 8 to 12) complexes find several applications in many areas of research, such as homogeneous/heterogeneous catalysis, advanced materials, chemical industry, and medicinal chemistry. Most current industrial chemical processes involve catalytic transformations via late transition metal complexes. This explains the attention of scientific research to this class of compounds. Late transition metal complexes catalyze many reactions, such as activation of C–H and C–C multiple bonds, olefin metathesis, hydrogenations, oxidations, epoxidations, cross coupling reactions, olefin hydroarylation, polymerizations, etc. They have several good properties that become apparent in the various fields in which they are used. Some features that should be emphasized are stability, selectivity, reactivity, facile synthesis, characterization. Ligands can significantly affect the reactivity and stability of metal complexes; in fact, their catalytic behavior can be easily modulated through modification of the stereoelectronic properties of ligands.

In this context, an important aspect in pharmacological research is represented by achieving new molecule-based metals, with lower toxicity and higher selectivity toward pathogenic microorganisms and cancer cells with respect to the drugs already used in clinical treatment. Recently, some metal complexes (platinum, gold, silver, ruthenium, etc.) are widely studied for their potential pharmacological activities as antibacterial and anticancer.

This Special Issue of Catalysts will highlights recent progress in terms of design, synthesis, characterization, and catalytic and/or pharmacological activity of late transition metal complexes.

Dr. Annaluisa Mariconda
Prof. Dr. Pasquale Longo
Guest Editors

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 submissions that pass pre-check are 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. Catalysts is an international peer-reviewed open access monthly 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 2700 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

late transition metal complexes
coordination chemistry
ligand design
late transition metal complexes biological activity
structure-activity relationship
catalysts based on late transition metals

Published Papers (7 papers)

Download All Papers

Research

Jump to: Review

16 pages, 3381 KiB

Open AccessArticle

Alternating Ring-Opening Metathesis Polymerization Promoted by Ruthenium Catalysts Bearing Unsymmetrical NHC Ligands

by Rubina Troiano, Chiara Costabile and Fabia Grisi

Catalysts 2023, 13(1), 34; https://doi.org/10.3390/catal13010034 - 24 Dec 2022

Cited by 3 | Viewed by 1451

Abstract

In this paper, Grubbs- and Hoveyda–Grubbs-type olefin metathesis catalysts featuring N-cyclopentyl/N’-mesityl backbone-substituted N-heterocyclic carbene (NHC) ligands were synthesized. Their propensity to promote the alternating ring-opening metathesis copolymerization (ROMP) of norbornene (NBE) with cyclooctene (COE) or cyclopentene (CPE) was evaluated and compared to that shown by analogous N-cyclohexyl complexes. High degrees of chemoselectivity were achieved in both copolymerizations. The presence of the N-cyclopentyl substituent allowed for the achievement of up to 98% and 97% of alternating diads for NBE-COE and NBE-CPE copolymers, respectively, at low comonomer ratios. Density functional theory (DFT) studies showed that both the sterical and electronic effects of NHC ligands influence catalyst selectivity. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Figure 1

7 pages, 2065 KiB

Open AccessArticle

A Calix[8]arene-Based Catalyst for Suzuki–Miyaura Couplings with Reduced Pd_Leaching

by Erika Adhel, Axel Labattut, Timothée Naret, Diana Dragoe and Vincent Huc

Catalysts 2022, 12(10), 1098; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101098 - 22 Sep 2022

Viewed by 1339

Abstract

Pd-catalysed reactions are amongst the most important in current chemistry. Consequently, very reactive catalysts were developed during the last decades, allowing very high conversions at low catalytic rates. However, decreasing Pd leaching in final products without decreasing catalyst efficiency remains an unsolved issue, especially in the pharma industry. We recently showed that using calixarenes as platforms for Pd-based catalysts constitutes an efficient answer to this concern. In the present work, we show that using these calixarenic platforms in combination with suitably engineered ligands allows for an even more strongly decreased Pd leaching. It thus opens up interesting perspectives for the synthesis of new families of catalysts combining a very high reactivity and a very low Pd leaching in final products. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Figure 1

12 pages, 3550 KiB

Open AccessArticle

A Novel Tri-Coordination Zinc Complex Functionalized Silicotungstate with ROS Catalytic Ability and Anti-Tumor Cells Activity

by Xiang Ma, Jiai Hua, Man Wang, Deqiang Zhang, Xinyao Pei, Xiaoyu Zhao, Yulan Niu and Yanqing Wang

Catalysts 2022, 12(7), 695; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12070695 - 24 Jun 2022

Cited by 3 | Viewed by 1516

Abstract

Reactive oxygen species (ROS) can be used as an effective method to treat tumors. Artificial oxidase has received increasing attention as a catalyst for ROS generation in fields ranging from bioinorganic chemistry to pharmaceutical chemistry. In this study, an artificial oxidase based on a binuclear zinc complex and Keggin-type silicotungstate [Zn₂(4,4′-bpy)(Phen)₂][SiW₁₂O₄₀] (ZSW) (4,4′-bpy = 4,4′-bipyridine; Phen = 1,10-phenanthroline) was synthesized and structurally featured in terms of its X-ray photoelectron spectrum (XPS), bond valence sum (Σs) calculation, IR spectra, and single-crystal X-ray diffraction (SXRD). ZSW is an ionic compound in which the cation is a binuclear zinc complex [Zn₂(4,4′-bpy)(Phen)₂]⁴⁺ and the anion is a α-Keggin-type silicotungstate [SiW₁₂O₄₀]^4– cluster. Notably, the Zn ions in the [Zn₂(4,4′-bpy)(Phen)₂] exist in tri-coordination, which was first obtained in polyoxometalate (POM) chemistry. It was also demonstrated that ZSW is capable of efficiently catalyzing the production of ROS, which, according to the computational calculations, may be due to the synergistic action of zinc complexes and POM building blocks. Furthermore, ZSW exhibited inhibition ability toward ROS-sensitive tumor cells, such as PC12 cells. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Figure 1

14 pages, 1049 KiB

Open AccessFeature PaperArticle

Catalytic and Biological Activity of Silver and Gold Complexes Stabilized by NHC with Hydroxy Derivatives on Nitrogen Atoms

by Marco Sirignano, Annaluisa Mariconda, Giovanni Vigliotta, Jessica Ceramella, Domenico Iacopetta, Maria Stefania Sinicropi and Pasquale Longo

Catalysts 2022, 12(1), 18; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010018 - 25 Dec 2021

Cited by 10 | Viewed by 2718

Abstract

In this paper is reported the synthesis of N,N′ hydroxy derivative of NHC silver (3a–4a) and gold(I) (3b–4b) complexes of general formula [M(NHC)₂]⁺ [MX₂]⁻. All [...] Read more.

In this paper is reported the synthesis of N,N′ hydroxy derivative of NHC silver (3a–4a) and gold(I) (3b–4b) complexes of general formula [M(NHC)₂]⁺ [MX₂]⁻. All compounds were characterized by spectroscopic and analytic techniques. The complexes turned out to be effective in both catalytic and biological applications. They catalyzed the coupling of aldehyde, piperidine, and phenylacetylene in A³-reaction to produce propargylamines and showed antimicrobial activity. In fact, minimal inhibition concentration (MIC) tests with Gram-positive and Gram-negative bacteria demonstrated that the silver compounds are selective toward E. coli, whereas the gold analogues are active against S. aureus. Moreover, the N,N′ hydroxy derivative of NHC silver complexes 3a and 4a exhibited good anticancer activity on the HeLA cancer cells (3a-IC₅₀ = 12.2 ± 0.1 µM, 4a-IC₅₀ = 11.9 ± 1.2 µM), whereas gold complex 4b displayed good anticancer activity towards the MCF-7 cells (IC₅₀ = 12.2 ± 1.2 µM). Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Figure 1

17 pages, 3188 KiB

Open AccessArticle

Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C₂B₉H₁₀]²⁻ and nido-[5,6-Me₂-7,8-C₂B₉H₉]²⁻ Dicarbollide Ligands

by Ivan D. Grishin, Anastasiya M. Zimina, Sergey A. Anufriev, Nadezhda A. Knyazeva, Alexander V. Piskunov, Fedor M. Dolgushin and Igor B. Sivaev

Catalysts 2021, 11(11), 1409; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111409 - 21 Nov 2021

Cited by 9 | Viewed by 1679

Abstract

The effect of methyl substituents in the lower belt of dicarbollide ligands on the redox potential of ruthenacarboranes based thereof, as well as the ability of the metallacarboranes obtained to catalyze radical polymerization with atom transfer were studied. For this purpose, a new approach to the synthesis of closo-ruthenacarboranes based on substituted dicarbollide ligands was developed and six new complexes 3,3-(Ph₂P(CH₂)₄PPh₂)-3-H-3-Cl-9-Me-12-X-closo-3,1,2-RuC₂B₉H₉, 3,3,8-(Ph₂P(CH₂)₄PPh-μ-(C₆H₄-o))-3-Cl-9-Me-12-X-closo-3,1,2-RuC₂B₉H₈ and 3,3,4,8-(Ph₂P(CH₂)₄P-μ-(C₆H₄-o)₂)-3-Cl-9-Me-9-X-closo-3,1,2-RuC₂B₉H₇ (X = H, Me) were synthetized and characterized by single crystal X-ray diffraction, NMR and ESR spectroscopy and MALDI TOF mass-spectrometry. Comparison of the values of the redox potentials of the synthesized ruthenium complexes in 1,2-dichloroethane with the values previously found for the corresponding ruthenacarboranes based on the parent dicarbollide anion showed that the introduction of methyl substituents into the carborane cage led to a decrease in the redox potentials of the complexes, which made them more preferable catalysts for ATRP. Test experiments on the polymerization of MMA showed that the synthesized ruthenacarboranes were effective catalysts for ATRP, the most active being the complex with two methyl groups and two ortho-phenylenecycloboronated fragments. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Graphical abstract

Review

Jump to: Research

46 pages, 18949 KiB

Open AccessFeature PaperReview

Recent Advances in N-Heterocyclic Carbene Coinage Metal Complexes in A³-Coupling and Carboxylation Reaction

by Assunta D’Amato, Marco Sirignano, Simona Russo, Rubina Troiano, Annaluisa Mariconda and Pasquale Longo

Catalysts 2023, 13(5), 811; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13050811 - 27 Apr 2023

Cited by 4 | Viewed by 1411

Abstract

Owing of their accessibility and wide range of reactivities, alkynes make for fascinating building blocks. Either a selective alkyne carbon-carbon triple bond reaction or activation of the terminal alkyne C-H bond may be employed to functionalize them. Monocationic coinage metal complexes with a d10 electronic configuration are effective catalysts for alkyne activation. Silver(I) and gold(I) N-heterocyclic (NHC) systems are emerging as promising catalysts in multicomponent alkyne activation reactions; this review paper focuses on A³ (aldehyde-amine-alkyne)-coupling reaction and carbon dioxide fixation, furnishing a systematic overview of the scientific advances achieved during the last two decades. This study will carefully compare the corresponding silver and gold complexes employed in the two processes. The differences in reaction routes brought about by the catalyst ligand structure will be investigated with an emphasis on evaluating the benefits provided by the easily tuneable NHC backbone, in terms of chemo- and stereo-selectivity. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures

Figure 1

31 pages, 8280 KiB

Open AccessReview

N-Heterocyclic Carbene Gold Complexes Active in Hydroamination and Hydration of Alkynes

by Annaluisa Mariconda, Marco Sirignano, Rubina Troiano, Simona Russo and Pasquale Longo

Catalysts 2022, 12(8), 836; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12080836 - 29 Jul 2022

Cited by 5 | Viewed by 2014

Abstract

Until the year 2000, gold compounds were considered catalytically inert. Subsequently, it was found that they are able to promote the nucleophilic attack on unsaturated substrates by forming an Au–π-system. The main limitation in the use of these catalytic systems is the ease with which they decompose, which is avoided by stabilization with an ancillary ligand. N-heterocyclic carbenes (NHCs), having interesting σ-donor capacities, are able to stabilize the gold complexes (Au (I/III) NHC), favoring the exploration of their catalytic activity. This review reports the state of the art (years 2007–2022) in the nucleophilic addition of amines (hydroamination) and water (hydration) to the terminal and internal alkynes catalyzed by N-heterocyclic carbene gold (I/III) complexes. These reactions are particularly interesting both because they are environmentally sustainable and because they lead to the production of important intermediates in the chemical and pharmaceutical industry. In fact, they have an atom economy of 100%, and lead to the formation of imines and enamines, as well as the formation of ketones and enols, all important scaffolds in the synthesis of bioactive molecules, drugs, heterocycles, polymers, and bulk and fine chemicals. Full article

(This article belongs to the Special Issue Late Transition Metal Complexes: Catalytic and/or Biological Activities)

► Show Figures