molecules-logo

Journal Browser

Journal Browser

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) | Viewed by 36155

Special Issue Editor

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenue Rovisco Pais, 1049-001 Lisbon, Portugal
Interests: computational chemistry; coordination chemistry; molecular catalysis; oxidation of hydrocarbons; activation of small molecules; reaction mechanism; chemical bond nature; cycloaddition; nitriles
Special Issues, Collections and Topics in MDPI journals

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 Previously unpublished manuscripts covering all experimental and theoretical aspects of metal mediated activation of small molecules are welcome for this Special Issue, including the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 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. 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 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

  • 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)

Order results
Result details
Select all
Export citation of selected articles as:

Research

2027 KiB  
Article
Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides
by Alexey N. Bilyachenko, Alexey I. Yalymov, Lidia S. Shul’pina, Dalmo Mandelli, Alexander A. Korlyukov, Anna V. Vologzhanina, Marina A. Es’kova, Elena S. Shubina, Mikhail M. Levitsky and Georgiy B. Shul’pin
Molecules 2016, 21(5), 665; https://doi.org/10.3390/molecules21050665 - 19 May 2016
Cited by 31 | Viewed by 6674
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)
Show Figures

Graphical abstract

1353 KiB  
Article
bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers
by Regina M. Islamova, Mikhail V. Dobrynin, Daniil M. Ivanov, Andrey V. Vlasov, Elena V. Kaganova, Galina V. Grigoryan and Vadim Yu. Kukushkin
Molecules 2016, 21(3), 311; https://doi.org/10.3390/molecules21030311 - 05 Mar 2016
Cited by 27 | Viewed by 7788
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)
Show Figures

Graphical abstract

2487 KiB  
Article
An Unusual Stress Metabolite from a Hydrothermal Vent Fungus Aspergillus sp. WU 243 Induced by Cobalt
by Chihong Ding, Xiaodan Wu, Bibi Nazia Auckloo, Chen-Tung Arthur Chen, Ying Ye, Kuiwu Wang and Bin Wu
Molecules 2016, 21(1), 105; https://doi.org/10.3390/molecules21010105 - 16 Jan 2016
Cited by 26 | Viewed by 6537
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)
Show Figures

Figure 1

2946 KiB  
Article
A Copper-Based Metal-Organic Framework as an Efficient and Reusable Heterogeneous Catalyst for Ullmann and Goldberg Type C–N Coupling Reactions
by Wei Long, Wenge Qiu, Chongwei Guo, Chuanqiang Li, Liyun Song, Guangmei Bai, Guizhen Zhang and Hong He
Molecules 2015, 20(12), 21178-21192; https://doi.org/10.3390/molecules201219756 - 27 Nov 2015
Cited by 15 | Viewed by 8147
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)
Show Figures

Graphical abstract

1083 KiB  
Article
Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks
by Luísa Martins, Rajendar Nasani, Manideepa Saha, Shaikh Mobin, Suman Mukhopadhyay and Armando Pombeiro
Molecules 2015, 20(10), 19203-19220; https://doi.org/10.3390/molecules201019203 - 21 Oct 2015
Cited by 22 | Viewed by 6336
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)
Show Figures

Graphical abstract

Back to TopTop