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Special Issue "Metal Mediated Activation of Small Molecules"

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

Deadline for manuscript submissions: closed (20 April 2016)

Special Issue Editor

Guest Editor
Dr. Maxim L. Kuznetsov

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisbon, Portugal
Website | E-Mail
Interests: computational chemistry, coordination chemistry, molecular catalysis, oxidation of hydrocarbons, activation of small molecules, reaction mechanism, chemical bond nature, cycloaddition, nitriles

Special Issue Information

Dear Colleagues,

Functionalization of inorganic and organic small molecules (water, molecular hydrogen, oxygen and nitrogen, carbon and nitrogen oxides, the simplest carbenes, carbynes, hydrocarbons, nitriles, isocyanides, and many others) is of tremendous importance for modern industrial and laboratory practices. Some of them may be used as abundant and cheap precursors for the synthesis of a great variety of compounds with valuable properties, or as promising sources of energy, while others are dangerous environmental pollutants, and their easy fixation may be a matter of survival for our society, at least, in its present state. However, many small molecules are rather thermodynamically inert, at least towards certain types of transformations, and, hence, they should be activated. Such activation may be efficiently achieved by the utilization of a metal center, which serves either as a catalyst or as a promoter. Previously unpublished manuscripts covering all experimental and theoretical aspects of metal mediated activation of small molecules are welcome for this Special Issue, including the development of new synthetic methods and optimization of reaction conditions, investigation of driving forces and factors determining the activation effects, and elucidation of the mechanistic details of the processes associated with the functionalization of small molecules of any type.

Dr. Maxim L. Kuznetsov
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 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 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

  • small molecules
  • activation
  • metal mediated reactions
  • reaction mechanism
  • transition metal complexes
  • pollutants
  • carbon monoxide
  • carbon dioxide
  • nitrogen oxides
  • water oxidation
  • oxygen
  • hydrogen
  • nitrogen fixation
  • hydrocarbons
  • oxidation
  • epoxidation

Published Papers (5 papers)

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Research

Open AccessArticle Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides
Molecules 2016, 21(5), 665; doi:10.3390/molecules21050665
Received: 12 April 2016 / Revised: 28 April 2016 / Accepted: 13 May 2016 / Published: 19 May 2016
Cited by 11 | PDF Full-text (2027 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)6(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)6(NaCl)(C4H8O2)13(PhCN)2(H2O)2 and studied by X-ray and
[...] Read more.
New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)6(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)6(NaCl)(C4H8O2)13(PhCN)2(H2O)2 and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers. Full article
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
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Open AccessArticle bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers
Molecules 2016, 21(3), 311; doi:10.3390/molecules21030311
Received: 1 February 2016 / Revised: 29 February 2016 / Accepted: 1 March 2016 / Published: 5 March 2016
Cited by 3 | PDF Full-text (1353 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C5H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co
[...] Read more.
cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C5H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl2(NCCH2Ph)2] exhibits the best catalytic activity (room temperature, c = 1.0 × 10−4 mol/L, τpot-life 60 min, τcuring 6 h). Although cis-[PtCl2(NCCH2Ph)2] is less active than the widely used Karstedt’s catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10−4 mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10−4–1.0 × 10−5 mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl2(NCR)2] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking. Full article
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
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Open AccessArticle An Unusual Stress Metabolite from a Hydrothermal Vent Fungus Aspergillus sp. WU 243 Induced by Cobalt
Molecules 2016, 21(1), 105; doi:10.3390/molecules21010105
Received: 16 December 2015 / Revised: 13 January 2016 / Accepted: 14 January 2016 / Published: 16 January 2016
Cited by 3 | PDF Full-text (2487 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A novel hybrid polyketide-terpenoid, aspergstressin (1), possessing a unique fused polycyclic structure, was induced from culture broth of strain Aspergillus sp. WU 243 by cobalt ion stimulation. The strain was isolated from the digestive gland of Xenograpsus testudinatus, a unique
[...] Read more.
A novel hybrid polyketide-terpenoid, aspergstressin (1), possessing a unique fused polycyclic structure, was induced from culture broth of strain Aspergillus sp. WU 243 by cobalt ion stimulation. The strain was isolated from the digestive gland of Xenograpsus testudinatus, a unique type of crab which dwells in the Kueishantao hydrothermal vents off Taiwan. The chemical structure and relative configuration of the stress metabolite were established by spectroscopic means. Aspergillus sp. WU 243 produced aspergstressin (1) only under cobalt stressed culture conditions. The results show that stress-driven discovery of new natural products from hydrothermal vent fungi is an effective strategy to unveil the untapped reservoir of small molecules from species found in the hydrothermal vent environment. Full article
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
Open AccessArticle A Copper-Based Metal-Organic Framework as an Efficient and Reusable Heterogeneous Catalyst for Ullmann and Goldberg Type C–N Coupling Reactions
Molecules 2015, 20(12), 21178-21192; doi:10.3390/molecules201219756
Received: 30 October 2015 / Revised: 13 November 2015 / Accepted: 17 November 2015 / Published: 27 November 2015
Cited by 4 | PDF Full-text (2946 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A highly porous metal-organic framework (Cu-TDPAT), constructed from a paddle-wheel type dinuclear copper cluster and 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT), has been tested in Ullmann and Goldberg type C–N coupling reactions of a wide range of primary and secondary amines with halobenzenes, affording the
[...] Read more.
A highly porous metal-organic framework (Cu-TDPAT), constructed from a paddle-wheel type dinuclear copper cluster and 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT), has been tested in Ullmann and Goldberg type C–N coupling reactions of a wide range of primary and secondary amines with halobenzenes, affording the corresponding N-arylation compounds in moderate to excellent yields. The Cu-TDPAT catalyst could be easily separated from the reaction mixtures by simple filtration, and could be reused at least five times without any significant degradation in catalytic activity. Full article
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
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Open AccessArticle Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks
Molecules 2015, 20(10), 19203-19220; doi:10.3390/molecules201019203
Received: 25 September 2015 / Revised: 13 October 2015 / Accepted: 16 October 2015 / Published: 21 October 2015
Cited by 5 | PDF Full-text (1083 KB) | HTML Full-text | XML Full-text
Abstract
Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate]has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II)
[...] Read more.
Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu33-4-ptz)42-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h−1), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 13 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity. Full article
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
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