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Catalysts
Special Issues
Ligand Design in Metal Chemistry: Reactivity and Catalysis
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Ligand Design in Metal Chemistry: Reactivity and Catalysis

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

Deadline for manuscript submissions: closed (20 October 2021) | Viewed by 9863

Special Issue Editors

Prof. Dr. Rita Mazzoni

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Guest Editor
Department of Industrial Chemistry "Toso Montanari", Università degli Studi di Bologna, 40136 Bologna, Italy
Interests: organometallic chemistry; ligand design; iron and ruthenium complexes; homogeneous catalysis; biomass valorization
Prof. Dr. Luca Rigamonti

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Guest Editor
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Modena e Reggio Emilia, 41125 Modena, Italy
Interests: coordination chemistry; electronic modulation; structure-property correlation studies; Schiff base ligands; magnetic properties
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Special Issue Information

Dear Colleagues,

Ligand design in organometallic and coordination chemistry represents a key point and one of the best ways for tuning properties of transition metal and lanthanide complexes. Indeed, by varying ligand nature and the relative steric hindrance of substituents, the electron density of the metal centre, as well as their catalytic activity and selectivity, can be efficiently driven. In addition to catalysis, this approach is optimal in all areas in which metal complexes can have an application thanks to their reactivity, such as responsive materials (e.g. magnetic or luminescent), bio-inorganic chemistry and sensing.

Within the aim of developing novel homogeneous catalysts and efficient processes, a great effort has to be devoted to sustainable objectives exploiting 3d transition metal reactivity and looking forward green transformation aimed to close life cycles. Ligand design plays also a fundamental role in filling the gap between homogeneous and heterogeneous catalysis toward the development of insoluble single-site supported catalysts.

This Special Issue aims to collect original research papers as well as reviews able to advance the knowledge in the rational design of ligands and their metal complexes, together with the study of the resulting reactivity and catalytic properties. Union between experimental and theoretical approaches are also welcome for this Special Issue.

Prof. Dr. Rita Mazzoni
Dr. Luca Rigamonti
Guest Editors

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. 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 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

  • Ligand design
  • Coordination ability
  • Electronic modulation
  • Homogeneous catalysis
  • Heterogeneous catalysis
  • Sustainable chemistry
  • Green conversion
  • Reactivity studies
  • Responsive materials

Published Papers (3 papers)

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Research

11 pages, 2374 KiB  
Article
Synthesis and Reactivity of Poly(propyleneimine) Dendrimers Functionalized with Cyclopentadienone N-Heterocyclic-Carbene Ruthenium(0) Complexes
by Cristiana Cesari, Riccardo Conti, Andrea Cingolani, Valerio Zanotti, Maria Cristina Cassani, Luca Rigamonti and Rita Mazzoni
Catalysts 2020, 10(2), 264; https://doi.org/10.3390/catal10020264 - 22 Feb 2020
Cited by 9 | Viewed by 3091
Abstract
Ligand design in metal chemistry is a fundamental step when pursuing compounds with specific reactivity. In this paper, the functionalization of the OH group in the lateral chain of the N-heterocyclic-carbene (NHC) ligand bound to a bis-carbonyl cyclopentadienone NHC ruthenium(0) complex [...] Read more.
Ligand design in metal chemistry is a fundamental step when pursuing compounds with specific reactivity. In this paper, the functionalization of the OH group in the lateral chain of the N-heterocyclic-carbene (NHC) ligand bound to a bis-carbonyl cyclopentadienone NHC ruthenium(0) complex allowed the decoration of five generations of poly(propyleneimine) (PPIs) dendrimers with up to 64 organometallic moieties. The coupling was achieved by employing carbonyldiimidazole and the formation of carbamate linkages between dendritic peripheral NH2 and lateral OH groups on ruthenium complexes. The synthetic procedure, chemical purification, and spectroscopic characterization of the five generations of dendrimers (3g1–5) are here described. The ruthenium-modified dendrimers were activated as catalysts in the transfer hydrogenation of the model compound 4-fluoroacetophenone in the presence of cerium ammonium nitrate as their mononuclear congeners. The catalytic activity, being similar for the five generations, shows a decrease if compared to mononuclear complexes. This detrimental effect might be ascribed to the –CH2NH– functionalization, largely present in dendrimer skeleton and that can compete with the hydrogen transfer mechanism, but also partially to a dendritic effect caused by steric encumbrance. Full article
(This article belongs to the Special Issue Ligand Design in Metal Chemistry: Reactivity and Catalysis)
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15 pages, 7163 KiB  
Article
Effects of Substitution Pattern in Phosphite Ligands Used in Rhodium-Catalyzed Hydroformylation on Reactivity and Hydrolysis Stability
by Svenja Kloß, Detlef Selent, Anke Spannenberg, Robert Franke, Armin Börner and Muhammad Sharif
Catalysts 2019, 9(12), 1036; https://doi.org/10.3390/catal9121036 - 06 Dec 2019
Cited by 9 | Viewed by 3637
Abstract
The stability of homogeneous catalytic systems is an industrially crucial topic, which, however, receives comparatively little attention from academic research. Phosphites are among the most frequently used ligands in industrial, rhodium-catalyzed n-regioselective hydroformylation. However, they are particularly vulnerable to hydrolysis. Since the [...] Read more.
The stability of homogeneous catalytic systems is an industrially crucial topic, which, however, receives comparatively little attention from academic research. Phosphites are among the most frequently used ligands in industrial, rhodium-catalyzed n-regioselective hydroformylation. However, they are particularly vulnerable to hydrolysis. Since the decomposition of ligands should be dependent on the substitution patterns, phenyl, tert-butyl and condensed ring systems of benzopinacolphosphites were evaluated concerning their activity, regioselectivity and hydrolysis stability. A series of twelve strongly related phosphites were synthesized, tested in the hydroformylation of isomeric n-octenes, and studied in hydrolysis experiments using in situ NMR spectroscopy. Our results show that substituents in the ortho-position, especially tert-butyl substituents, enhance hydrolysis stability while maintaining compelling activity and regioselectivity. In contrast, substituents in the para-position may destabilize the phosphite. Full article
(This article belongs to the Special Issue Ligand Design in Metal Chemistry: Reactivity and Catalysis)
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18 pages, 2222 KiB  
Article
Synthesis, Characterization, Solution Behavior and Theoretical Studies of Pd(II) Allyl Complexes with 2-Phenyl-3H-indoles as Ligands
by Maria Tomé, Arnald Grabulosa, Mercè Rocamora, Gabriel Aullón, Mercè Font-Bardía, Teresa Calvet and Concepción López
Catalysts 2019, 9(10), 811; https://doi.org/10.3390/catal9100811 - 27 Sep 2019
Cited by 1 | Viewed by 2298
Abstract
The study of the reactivity of three 2-phenyl-3H-indole ligands of general formulae C8H3N-2-(C6H4-4-R1)-3-NOMe-5-R2 (1) [with R1 = H, R2 = OMe (a); R1 [...] Read more.
The study of the reactivity of three 2-phenyl-3H-indole ligands of general formulae C8H3N-2-(C6H4-4-R1)-3-NOMe-5-R2 (1) [with R1 = H, R2 = OMe (a); R1 = R2 = H (b) or R1 = Cl, R2 = H (c)] with [Pd(η3-1-R3C3H4)(μ-Cl)]2 (R3 = H or Ph) has allowed us to isolate two sets of new Pd(II)-allyl complexes of general formulae [Pd(η3-1-R3C3H4)(1)Cl] {R3 = H (2) or Ph (3)}. Compounds 2a–2c and 3a–3c were characterized by elemental analyses, mass spectrometry and IR spectroscopy. The crystal structures of 2a, 3a and 3b were also determined by X-ray diffraction. 1H-NMR studies reveal the coexistence of two (for 2a–2c) or three (for 3a–3c) isomeric forms in CD2Cl2 solutions at 182 K. Additional studies on the catalytic activity of mixtures containing [Pd(η3-C3H5)(μ-Cl)]2 and the parent ligand (1a–1c) in the allylic alkylation of (E)-3-phenyl-2-propenyl (cinnamyl) acetate with sodium diethyl 2-methylmalonate as well as the stoichiometric reaction between compounds 3a and 3c with the nucleophile reveal that in both cases the formation of the linear trans- derivative is strongly preferred over the branched product. Computational studies at a DFT level on compound 3a allowed us to compare the relative stability of their isomeric forms present in solution and to explain the regioselectivity of the catalytic and stoichiometric processes. Full article
(This article belongs to the Special Issue Ligand Design in Metal Chemistry: Reactivity and Catalysis)
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