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Metal-Induced Molecule Activation and Coupling Reactions

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

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 11286

Special Issue Editors


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Guest Editor
1. Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2. University of Chinese Academy of Sciences, Beijing, China
Interests: homogeneous catalysis; ethylene polymerization; organometallic chemistry; coordination chemistry; polymer science

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Guest 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
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Special Issue Information

Dear Colleagues,

It is my pleasure to invite you to contribute a manuscript to an upcoming Special Issue of Molecules on “Metal-Induced Molecular Activation and Coupling Reactions”. This Special Issues wishes to explore the ever-expanding subject of molecular activation for creating active sites to conduct coupling reactions, in which any of the functional sites of the activated molecule may be further used to form new molecules. To speed up the reaction and reduce the formation of byproducts, chemists have employed metal as media, which is involved in the formation of organometallic intermediates that promote reaction as well as the formation and activity of catalytic species in homogeneous catalysis. The intention of this issue is to capture the state-of-the-art of metal-promoting coupling reactions, either as mechanistic studies or new reactions, in order to enhance development of new molecules as well as chemical applications in providing building blocks for materials science and chemical drugs. Besides the rapid development of nano and biochemical sciences, the importance and performance of the chemistry and its application still lie at the cutting edge when it comes to the development of new techniques—transforming cheaper substrates into fine chemicals, converting chemicals into functional molecules, and linking small molecules into materials. Your contributions would be highly appreciated in promoting understand of this chemistry and its applications in outlining the latest scientific progress in this area. Furthermore, Molecules is a premier journal which offers a perfect venue for the rapid publication of original and review articles on the topics of molecule transformation, new molecule synthesis, and their applications.

Dr. Wen-Hua Sun

Dr. Maxim L. Kuznetsov

Guest Editors

Manuscript Submission Information

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Keywords

  • metal–carbon bonding
  • coupling reaction
  • organometallic compound
  • homogeneous catalysis
  • transformation of small molecules

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Published Papers (4 papers)

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Research

18 pages, 7431 KiB  
Article
Sequential Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Chlorobenzamides/Chemoselective Amide Reduction and Reductive Deuteration to Benzylic Alcohols
by Elwira Bisz, Pamela Podchorodecka, Hengzhao Li, Wioletta Ochędzan-Siodłak, Jie An and Michal Szostak
Molecules 2023, 28(1), 223; https://doi.org/10.3390/molecules28010223 - 27 Dec 2022
Viewed by 2651
Abstract
Benzylic alcohols are among the most important intermediates in organic synthesis. Recently, the use of abundant metals has attracted significant attention due to the issues with the scarcity of platinum group metals. Herein, we report a sequential method for the synthesis of benzylic [...] Read more.
Benzylic alcohols are among the most important intermediates in organic synthesis. Recently, the use of abundant metals has attracted significant attention due to the issues with the scarcity of platinum group metals. Herein, we report a sequential method for the synthesis of benzylic alcohols by a merger of iron catalyzed cross-coupling and highly chemoselective reduction of benzamides promoted by sodium dispersion in the presence of alcoholic donors. The method has been further extended to the synthesis of deuterated benzylic alcohols. The iron-catalyzed Kumada cross-coupling exploits the high stability of benzamide bonds, enabling challenging C(sp2)–C(sp3) cross-coupling with alkyl Grignard reagents that are prone to dimerization and β-hydride elimination. The subsequent sodium dispersion promoted reduction of carboxamides proceeds with full chemoselectivity for the C–N bond cleavage of the carbinolamine intermediate. The method provides access to valuable benzylic alcohols, including deuterium-labelled benzylic alcohols, which are widely used as synthetic intermediates and pharmacokinetic probes in organic synthesis and medicinal chemistry. The combination of two benign metals by complementary reaction mechanisms enables to exploit underexplored avenues for organic synthesis. Full article
(This article belongs to the Special Issue Metal-Induced Molecule Activation and Coupling Reactions)
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20 pages, 4347 KiB  
Article
Unifying Molecular Weights of Highly Linear Polyethylene Waxes through Unsymmetrical 2,4-Bis(imino)pyridylchromium Chlorides
by Badral Gansukh, Qiuyue Zhang, Chantsalnyam Bariashir, Arumugam Vignesh, Yanping Ma, Tongling Liang and Wen-Hua Sun
Molecules 2020, 25(23), 5584; https://doi.org/10.3390/molecules25235584 - 27 Nov 2020
Cited by 2 | Viewed by 2461
Abstract
By dealing CrCl3∙3THF with the corresponding ligands (L1L5), an array of fluoro-substituted chromium (III) chlorides (Cr1Cr5) bearing 2-[1-(2,4-dibenzhydryl-6-fluoro- phenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine (aryl = 2,6-Me2Ph Cr1, 2,6-Et2Ph Cr2, 2,6-iPr2 [...] Read more.
By dealing CrCl3∙3THF with the corresponding ligands (L1L5), an array of fluoro-substituted chromium (III) chlorides (Cr1Cr5) bearing 2-[1-(2,4-dibenzhydryl-6-fluoro- phenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine (aryl = 2,6-Me2Ph Cr1, 2,6-Et2Ph Cr2, 2,6-iPr2Ph Cr3, 2,4,6-Me3Ph Cr4, 2,6-Et2-4-MePh Cr5) was synthesized in good yield and validated via Fourier Transform Infrared (FT-IR) spectroscopy and elemental analysis. Besides the routine characterizations, the single-crystal X-ray diffraction study revealed the solid-state structures of complexes Cr2 and Cr4 as the distorted-octahedral geometry around the chromium center. Activated by either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the chromium catalysts exhibited high activities toward ethylene polymerization with the MMAO-promoted polymerizations far more productive than with MAO (20.14 × 106 g (PE) mol−1 (Cr) h−1 vs. 10.03 × 106 g (PE) mol−1 (Cr) h−1). In both cases, the resultant polyethylenes were found as highly linear polyethylene waxes with low molecular weights around 1–2 kg mol−1 and narrow molecular weight distribution (MWD range: 1.68–2.25). In general, both the catalytic performance of the ortho-fluorinated chromium complexes and polymer properties have been the subject of a detailed investigation and proved to be highly dependent on the polymerization reaction parameters (including cocatalyst type and amount, reaction temperature, ethylene pressure and run time). Full article
(This article belongs to the Special Issue Metal-Induced Molecule Activation and Coupling Reactions)
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16 pages, 5113 KiB  
Article
Water-Soluble O-, S- and Se-Functionalized Cyclic Acetyl-triaza-phosphines. Synthesis, Characterization and Application in Catalytic Azide-alkyne Cycloaddition
by Abdallah G. Mahmoud, Piotr Smoleński, M. Fátima C. Guedes da Silva and Armando J. L. Pombeiro
Molecules 2020, 25(22), 5479; https://doi.org/10.3390/molecules25225479 - 23 Nov 2020
Cited by 11 | Viewed by 2919
Abstract
The 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) derivatives, viz. the already reported 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 5-oxide (DAPTA=O, 1), the novel 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-sulfide (DAPTA=S, 2), and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-selenide (DAPTA=Se, 3), have been synthesized under mild conditions. They are soluble in water and most common organic solvents and have been [...] Read more.
The 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) derivatives, viz. the already reported 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 5-oxide (DAPTA=O, 1), the novel 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-sulfide (DAPTA=S, 2), and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane-5-selenide (DAPTA=Se, 3), have been synthesized under mild conditions. They are soluble in water and most common organic solvents and have been characterized using 1H and 31P NMR spectroscopy and, for 2 and 3, also by single crystal X-ray diffraction. The effect of O, S, or Se at the phosphorus atom on the structural features of the compounds has been investigated, also through the analyses of Hirshfeld surfaces. The presence of 13 enhances the activity of copper for the catalytic azide-alkyne cycloaddition reaction in an aqueous medium. The combination of cheaply available copper (II) acetate and compound 1 has been used as a catalyst for the one-pot and 1,4-regioselective procedure to obtain 1,2,3-triazoles with high yields and according to ‘click rules’. Full article
(This article belongs to the Special Issue Metal-Induced Molecule Activation and Coupling Reactions)
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17 pages, 2512 KiB  
Article
6-Arylimino-2-(2-(1-phenylethyl)naphthalen-1-yl)-iminopyridylmetal (Fe and Co) Complexes as Highly Active Precatalysts for Ethylene Polymerization: Influence of Metal and/or Substituents on the Active, Thermostable Performance of Their Complexes and Resultant Polyethylenes
by Wenhua Lin, Liping Zhang, Jiahao Gao, Qiuyue Zhang, Yanping Ma, Hua Liu and Wen-Hua Sun
Molecules 2020, 25(18), 4244; https://doi.org/10.3390/molecules25184244 - 16 Sep 2020
Cited by 13 | Viewed by 2283
Abstract
A series of 6-arylimino-2-(2-(1-phenylethyl)naphthalen-1-yl)iminopyridines and their iron(II) and cobalt(II) complexes (Fe1Fe5, Co1Co5) were synthesized and routinely characterized as were Co3 and Co5 complexes, studied by single crystal X-ray crystallography, which individually displayed a distorted square pyramidal [...] Read more.
A series of 6-arylimino-2-(2-(1-phenylethyl)naphthalen-1-yl)iminopyridines and their iron(II) and cobalt(II) complexes (Fe1Fe5, Co1Co5) were synthesized and routinely characterized as were Co3 and Co5 complexes, studied by single crystal X-ray crystallography, which individually displayed a distorted square pyramidal or trigonal bipyramid around a cobalt center. Upon treatment with either methyluminoxane (MAO) or modified methyluminoxane (MMAO), all complexes displayed high activities regarding ethylene polymerization even at an elevated temperature, enhancing the thermostability of the active species. In general, iron precatalysts showed higher activities than their cobalt analogs; for example, 10.9 × 106 g(PE) mol−1 (Co) h−1 by Co4 and 17.0 × 106 g(PE) mol−1 (Fe) h−1 by Fe4. Bulkier substituents are favored for increasing the molecular weights of the resultant polyethylenes, such as 25.6 kg mol−1 obtained by Co3 and 297 kg mol−1 obtained by Fe3. A narrow polydispersity of polyethylenes was observed by iron precatalysts activated by MMAO, indicating a single-site active species formed. Full article
(This article belongs to the Special Issue Metal-Induced Molecule Activation and Coupling Reactions)
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