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Inorganics
Special Issues
Bond Activation and Catalysis Using Main-Group Elements
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Bond Activation and Catalysis Using Main-Group Elements

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 16217

Special Issue Editor

Dr. Jianbing "Jimmy" Jiang

E-Mail Website
Guest Editor
Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221, USA
Interests: electrocatalysis; main-group element catalysis; electrochemical energy storage; redox flow batteries

Special Issue Information

Dear Colleagues,                                        

Molecular catalysis represents one of the major categories in the broad catalysis field. Molecular catalysis research has primarily focused on transition metal-based catalysts owing to their high catalytic efficiency and activity. The success of transition-metal catalysis is attributed to the transition metal’s valence d-orbitals and unique interaction between metals and ligands, resulting in important features such as fast redox kinetics. However, the use of transition metals may also raise issues related to sustainability, such as high cost and high toxicity, which has prompted the research for alternative catalytic systems that offer comparable or higher catalytic activities with fewer drawbacks. The advancement of main-group element catalysts with comparable catalytic efficiency and activity is a critical step towards widespread use of main-group elements in bond activation and catalysis. This Special Issue aims to collect research articles and critical reviews that highlight recent advances in the broad field of main-group element-based bond activation and catalysis.

Dr. Jianbing "Jimmy" Jiang
Guest Editor

Manuscript Submission Information

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Keywords

  • Main-group element catalysis
  • Main-group element chemistry
  • Bond activation
  • Electrocatalysis

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Published Papers (3 papers)

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Research

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14 pages, 4256 KiB  
Article
Oxo-Stabilised Phosphonium Ylides as Hydrogen Bond Acceptors
by R. Alan Aitken, Lee P. Cleghorn, Graham Dawson, Ian P. Gray, Anna Lashtabeg and Alexandra M. Z. Slawin
Inorganics 2023, 11(2), 50; https://doi.org/10.3390/inorganics11020050 - 18 Jan 2023
Viewed by 1566
Abstract
Oxo-stabilised phosphonium ylides are found to form crystalline hydrogen-bonded adducts with aromatic carboxylic acids, as confirmed by X-ray diffraction. There is also strong hydrogen bonding in solution as indicated by 13C NMR spectroscopy and this confirmed adduct formation with acetic acid, benzamide, [...] Read more.
Oxo-stabilised phosphonium ylides are found to form crystalline hydrogen-bonded adducts with aromatic carboxylic acids, as confirmed by X-ray diffraction. There is also strong hydrogen bonding in solution as indicated by 13C NMR spectroscopy and this confirmed adduct formation with acetic acid, benzamide, thiobenzamide, benzyl alcohol, benzenesulfinic acid and diphenylphosphinic acid. The X-ray structure of the benzamide adduct was also determined, showing a hydrogen-bonded dimeric structure. A bis(stabilised ylide) was also prepared and is found to form a complex hydrogen-bonded adduct with benzoic acid, ethanol and water. Full article
(This article belongs to the Special Issue Bond Activation and Catalysis Using Main-Group Elements)
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17 pages, 5251 KiB  
Article
Phenolic 3° Phosphine Oxides as a Class of Metal-Free Catalysts for the Activation of C–O Bonds in Aliphatic Alcohols: Direct Synthesis of Catalyst Candidates, and Kinetic Studies
by Matthew A. Martin, Sadie L. Brown, Danielle R. Beres, Wrebekah M. Frederic, Ashley M. Banks and Aaron J. Bloomfield
Inorganics 2022, 10(3), 35; https://doi.org/10.3390/inorganics10030035 - 11 Mar 2022
Cited by 2 | Viewed by 4511
Abstract
It was recently reported that a (2-hydroxybenzyl)phosphine oxide (2-HOBPO) can serve as a phosphorus-centered catalyst for the stereo-invertive coupling of aliphatic alcohols and acidic pronucleophiles (akin to a Mitsunobu reaction, but without additional reagents). Herein, we report an improved synthesis, which provides direct [...] Read more.
It was recently reported that a (2-hydroxybenzyl)phosphine oxide (2-HOBPO) can serve as a phosphorus-centered catalyst for the stereo-invertive coupling of aliphatic alcohols and acidic pronucleophiles (akin to a Mitsunobu reaction, but without additional reagents). Herein, we report an improved synthesis, which provides direct access to systematically varied 2-HOBPOs in a single step from commercially available precursors (salicylaldehydes and secondary phosphines). The efficiency and generality of the synthetic method enabled limited structure–activity relationship (SAR) studies, from which it was determined that substituents on both the phenolic and phosphine oxide portions can exert significant influence on the turnover frequency (TOF) of each catalyst. Importantly, for all catalytically active 2-HOBPOs examined, the molecularity of catalyst in the rate law of the alcohol coupling was determined to be <1. Thus, for high catalyst loadings, differences in catalytic activity between 2-HOBPOs appear to be dominated by differences in catalytic auto-inhibition, while for low catalyst loadings, differences are attributed to inherent differences in the energetic span of the catalytic cycle, ignoring off-cycle species, in good agreement with density functional theory (DFT) modeling at the ωB97X-D/6-311G(d,p) level. Full article
(This article belongs to the Special Issue Bond Activation and Catalysis Using Main-Group Elements)
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Review

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30 pages, 4444 KiB  
Review
Coumarins Synthesis and Transformation via C–H Bond Activation—A Review
by Katarzyna Szwaczko
Inorganics 2022, 10(2), 23; https://doi.org/10.3390/inorganics10020023 - 15 Feb 2022
Cited by 19 | Viewed by 8766
Abstract
For several decades, coumarins have attracted considerable attention due to the fact of their application in diverse fields such as medical science and biomedical research as well as several industrial branches. Recently, many compounds containing the coumarin moiety have been intensively studied, mainly [...] Read more.
For several decades, coumarins have attracted considerable attention due to the fact of their application in diverse fields such as medical science and biomedical research as well as several industrial branches. Recently, many compounds containing the coumarin moiety have been intensively studied, mainly due to the fact of their biological activities such as antitumor, antioxidative, anti-HIV, vasorelaxant, antimicrobial, and anticancer. They are also widely used as fluorescent dyes and probes because of their great structural flexibility and large fluorescent quantum yields. For this reason, numerous attempts have been made to develop new and more practical methods for the synthesis of these compounds. This review aims at providing a comprehensive overview of coumarin synthesis methods by direct C–H bond activation in order to demonstrate the current state-of-the-art methods as well as the current limitations. Full article
(This article belongs to the Special Issue Bond Activation and Catalysis Using Main-Group Elements)
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