Special Issue "Catalysis Assisted by Calculations: From Organic and Metal Catalysts to Enzymes"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: closed (31 October 2017)

Special Issue Editor

Guest Editor
Dr. Albert Poater

Institute of Computational Chemistry and Catalysis (IQCC), Universitat de Girona, Campus de Montilivi sn, 17071 Girona, Spain
Website | E-Mail
Phone: (+34) 972418358
Fax: (+34) 972418356
Interests: homogeneous catalysis; organometallic chemistry; DFT calculations; computational chemistry; coordination chemistry; NHC-metal complexes; ruthenium based olefin metathesis; gold chemistry; hydrogenation by iron catalysts

Special Issue Information

Dear Colleagues,

Catalysis can be defined as “the causing or accelerating of a chemical change by the addition of a catalyst” and ab initio static or molecular dynamics calculations can be the right tool to face new challenges in science, saving time and experiments. Calculations can generate in silico predictions that then can be tested experimentally. Thus, nowadays, calculations could be defined as one of the catalysts of science. Even though, when we hear about catalysts we automatically think about metal catalysts, organic catalysts that are able to fix CO2 or in silico enzymes that mimethize biological reactions are the present and future of catalysis as well.

This Special Issue aims is to gather the different approaches to catalysis assisted by calculations. Contributions dealing with catalyst development, synthesis, and applications in organic, inorganic and polymer chemistry, biological enzymes, and green processes are particularly welcome. All in all, mechanistic studies and theoretical investigations should demonstrate that they are not only a tool, but a solution to face new challenges in catalysis, with predictions before experiments. Research papers, as well as reviews or perspectives, are welcome.

Dr. Albert Poater
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. 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 1300 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

  • in silico enzymes
  • catalyst development
  • organic catalyst
  • organometallic chemistry
  • metal catalyst
  • calculations
  • DFT
  • mechanistic studies
  • theoretical investigations

Published Papers (3 papers)

View options order results:
result details:
Displaying articles 1-3
Export citation of selected articles as:

Research

Open AccessFeature PaperArticle Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism
Catalysts 2017, 7(12), 388; doi:10.3390/catal7120388
Received: 14 November 2017 / Revised: 7 December 2017 / Accepted: 11 December 2017 / Published: 13 December 2017
PDF Full-text (2603 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and
[...] Read more.
Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH2), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition–Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving CuIII intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity. Full article
Figures

Open AccessArticle Racemization of Serine Residues Catalyzed by Dihydrogen Phosphate Ion: A Computational Study
Catalysts 2017, 7(12), 363; doi:10.3390/catal7120363
Received: 26 October 2017 / Revised: 16 November 2017 / Accepted: 22 November 2017 / Published: 27 November 2017
PDF Full-text (2179 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Spontaneous, nonenzymatic reactions in proteins are known to have relevance to aging and age-related diseases, such as cataract and Alzheimer’s disease. Among such reactions is the racemization of Ser residues, but its mechanism in vivo remains to be clarified. The most likely intermediate
[...] Read more.
Spontaneous, nonenzymatic reactions in proteins are known to have relevance to aging and age-related diseases, such as cataract and Alzheimer’s disease. Among such reactions is the racemization of Ser residues, but its mechanism in vivo remains to be clarified. The most likely intermediate is an enol. Although being nonenzymatic, the enolization would need to be catalyzed to occur at a biologically relevant rate. In the present study, we computationally found plausible reaction pathways for the enolization of a Ser residue where a dihydrogen phosphate ion, H2PO4, acts as a catalyst. The H2PO4 ion mediates the proton transfer required for the enolization by acting simultaneously as both a general base and a general acid. Using the B3LYP density functional theory method, reaction pathways were located in the gas phase and hydration effects were evaluated by single-point calculations using the SM8 continuum model. The activation barriers calculated for the reaction pathways found were around 100 kJ mol−1, which is consistent with spontaneous reactions occurring at physiological temperature. Our results are also consistent with experimental observations that Ser residue racemization occurs more readily in flexible regions in proteins. Full article
Figures

Figure 1

Open AccessArticle Mechanistic Insight into the 2° Alcohol Oxidation Mediated by an Efficient CuI/L-Proline-TEMPO Catalyst—A Density Functional Theory Study
Catalysts 2017, 7(9), 264; doi:10.3390/catal7090264
Received: 10 August 2017 / Revised: 31 August 2017 / Accepted: 31 August 2017 / Published: 5 September 2017
PDF Full-text (4929 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Density functional theory (DFT) calculations have been performed to investigate the 2° alcohol oxidation to acetophenone catalyzed by the CuI/L-Proline-2,2,6,6- tetramethylpiperidinyloxy (TEMPO) catalyst system. Seven possible pathways (paths A→F) are presented. Our calculations show that two pathways (path A and path
[...] Read more.
Density functional theory (DFT) calculations have been performed to investigate the 2° alcohol oxidation to acetophenone catalyzed by the CuI/L-Proline-2,2,6,6- tetramethylpiperidinyloxy (TEMPO) catalyst system. Seven possible pathways (paths A→F) are presented. Our calculations show that two pathways (path A and path B) are the potential mechanisms. Furthermore, by comparing with experimental observation, it is found that path A—in which substrate alcohol provides the proton to OtBu to produce HOtBu followed by the oxidation of substrate directly to product acetophenone by O2—is favored in the absence of TEMPO. Correspondingly, path B is likely to be favored when TEMPO is involved. In path B, the O–O bond cleavage of CuI–OOH to CuII–OH species occurs, followed by acetophenone formation assisted by ligand (L)2ˉ. It is also found that the cooperation of ligand (L)2ˉ and TEMPO plays an important role in assisting the formation of the product acetophenone in path B. Full article
Figures

Back to Top