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Exclusive Feature Papers in Organometallic Chemistry
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Exclusive Feature Papers in Organometallic Chemistry

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

Deadline for manuscript submissions: closed (15 November 2021) | Viewed by 28622

Special Issue Editors

Dr. Maurizio Peruzzini

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Guest Editor
Consiglio Nazionale delle Ricerche (CNR) Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, FI, Italy
Interests: activation and functionalization of elemental phosphorus; activation of small inorganic and organic molecules; transition-metal hydrides and molecular hydrogen chemistry; materials for H-storage; carbon dioxide capture and valorization
Special Issues, Collections and Topics in MDPI journals
Dr. Luca Gonsalvi

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Guest Editor
Institute of Chemistry of Organometallic Compounds, National Research Council of Italy (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy
Interests: organometallics and catalysis in water and biphasic systems; CO2 activation and utilization processes; hydrogen activation, production, and storage by organometallics; homogeneous catalysis; catalytic mechanisms
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

We are pleased to announce a Special Issue entitled “Exclusive Feature Papers in Organometallic Chemistry.” This is a collection of important high-quality papers (original research articles or comprehensive review papers) published in open-access format by Editorial Board Members or prominent scholars invited by the Editorial Office and the Guest Editors. This Special Issue aims to discuss new knowledge or new cutting-edge developments in the Organometallic Chemistry research field through selected works, in the hope of making a great contribution to the community. We intend for this Issue to be the best forum for disseminating excellent research findings as well as sharing innovative ideas in the field.

Prof. Dr. Maurizio Peruzzini
Prof. Dr. Luca Gonsalvi
Guest Editors

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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

  • organometallic chemistry
  • organometallics
  • metal complexes

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Published Papers (9 papers)

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Research

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12 pages, 1782 KiB  
Article
Efficient Catalytic Reduction of 4-Nitrophenol Using Copper(II) Complexes with N,O-Chelating Schiff Base Ligands
by Hassan Wafi Garba, Muhammad Sabiu Abdullahi, Mohamad Shazwan Shah Jamil and Nor Azam Endot
Molecules 2021, 26(19), 5876; https://doi.org/10.3390/molecules26195876 - 28 Sep 2021
Cited by 10 | Viewed by 3222
Abstract
The reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride was used as a model to test the catalytic activity of copper(II) complexes containing N,O-chelating Schiff base ligands. In this study, a series of copper(II) complexes containing respective Schiff base ligands, N′-salicylidene-2-aminophenol ( [...] Read more.
The reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride was used as a model to test the catalytic activity of copper(II) complexes containing N,O-chelating Schiff base ligands. In this study, a series of copper(II) complexes containing respective Schiff base ligands, N′-salicylidene-2-aminophenol (1), N′-salicylidene-2-aminothiazole (2), and N,N′-bis(salicylidene)-o-phenylenediamine (3), were synthesized and characterized by elemental analysis, Fourier transform infrared (FT-IR), UV-Visible (UV-Vis) and electron paramagnetic resonance (EPR) spectroscopies. The results from the 4-nitrophenol reduction showed that 3 has the highest catalytic activities with 97.5% conversion, followed by 2 and 1 with 95.2% and 90.8% conversions, respectively. The optimization of the catalyst amount revealed that 1.0 mol% of the catalyst was the most optimized amount with the highest conversion compared to the other doses, 0.5 mol% and 1.5 mol%. Recyclability and reproducibility tests confirmed that all three complexes were active, efficient, and possess excellent reproducibility with consistent catalytic performances and could be used again without a major decrease in the catalytic activity. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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26 pages, 42966 KiB  
Article
Replacement of Volatile Acetic Acid by Solid SiO2@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand
by Yun Wang, Florence Gayet, Jean-Claude Daran, Pascal Guillo and Dominique Agustin
Molecules 2021, 26(18), 5435; https://doi.org/10.3390/molecules26185435 - 7 Sep 2021
Cited by 2 | Viewed by 2841
Abstract
Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CH3COOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by SiO2 (nano)particles with two different sizes to which [...] Read more.
Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CH3COOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by SiO2 (nano)particles with two different sizes to which pending carboxylic functions were added (SiO2@COOH). The SiO2@COOH beads were obtained by the functionalization of SiO2 with pending nitrile functions (SiO2@CN) followed by CN hydrolysis. All complexes and silica beads were characterized by NMR, infrared, DLS, TEM, X-ray diffraction. The replacement of CH3COOH by SiO2@COOH (100 times less on molar ratio) has been evaluated for (ep)oxidation on several substrates (cyclooctene, cyclohexene, cyclohexanol) and discussed in terms of activity and green metrics. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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10 pages, 9451 KiB  
Article
Some Novel Cobalt Diphenylphosphine Complexes: Synthesis, Characterization, and Behavior in the Polymerization of 1,3-Butadiene
by Giovanni Ricci, Giuseppe Leone, Giorgia Zanchin, Benedetta Palucci, Alessandra Forni, Anna Sommazzi, Francesco Masi, Stefano Zacchini, Massimo Guelfi and Guido Pampaloni
Molecules 2021, 26(13), 4067; https://doi.org/10.3390/molecules26134067 - 2 Jul 2021
Cited by 4 | Viewed by 2291
Abstract
Some novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with (2-methoxyethyl)diphenylphosphine, (2-methoxyphenyl)diphenylphosphine, and 2-(1,1-dimethylpropyl)-6-(diphenylphosphino)pyridine. Single crystals suitable for X-ray diffraction studies were obtained for the first two complexes, and their crystal structure was determined. The novel compounds were then used in [...] Read more.
Some novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with (2-methoxyethyl)diphenylphosphine, (2-methoxyphenyl)diphenylphosphine, and 2-(1,1-dimethylpropyl)-6-(diphenylphosphino)pyridine. Single crystals suitable for X-ray diffraction studies were obtained for the first two complexes, and their crystal structure was determined. The novel compounds were then used in association with methylaluminoxane (MAO) for the polymerization of 1,3-butadiene, and their behavior was compared with that exhibited in the polymerization of the same monomer by the systems CoCl2(PnPrPh2)2/MAO and CoCl2(PPh3)2/MAO. Some significant differences were observed depending on the MAO/Co ratio used, and a plausible interpretation for such a different behavior is proposed. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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20 pages, 1922 KiB  
Article
Meloxicam and Study of Their Antimicrobial Effects against Phyto- and Human Pathogens
by Hazem S. Elshafie, Sadeek A. Sadeek, Wael A. Zordok and Amira A. Mohamed
Molecules 2021, 26(5), 1480; https://doi.org/10.3390/molecules26051480 - 9 Mar 2021
Cited by 14 | Viewed by 2708
Abstract
Recently, the design of new biological metal-ligand complexes has gained a special interest all over the world. In this research, new series of mixed ligand complexes from meloxicam (H2mel) and glycine (Gly) were synthesized. Structures of the compounds were investigated employing [...] Read more.
Recently, the design of new biological metal-ligand complexes has gained a special interest all over the world. In this research, new series of mixed ligand complexes from meloxicam (H2mel) and glycine (Gly) were synthesized. Structures of the compounds were investigated employing elemental analyses, infrared, electronic absorption, 1H NMR, thermal analyses, effective magnetic moment and conductivity. The estimated molar conductivity of the compounds in 1 × 10−3 M DMF solution indicates the non-electrolyte existence of the examined complexes. Additionally, the effective magnetic moment values refer to the complexes found as octahedral molecular geometry. The data of the infrared spectra showed the chelation of H2mel and Gly with metal ions from amide oxygen and nitrogen of the thyizol groups of H2mel and through nitrogen of the amide group and oxygen of the carboxylic group for Gly. Thermal analyses indicated that the new complexes have good thermal stability and initially lose hydration water molecules followed by coordinated water molecules, Gly and H2mel. The kinetic parameters were calculated graphically using Coats–Redfern and Horowitz–Metzeger methods at n = 1 and n ≠ 1. The density functional theory (DFT) calculations were performed at B3LYP levels. The optimized geometry of the ligand and its complexes were obtained based on the optimized structures. The data indicated that the complexes are soft with η value in the range 0.114 to 0.086, while η = 0.140 for free H2mel. The new prepared complexes were investigated as antibacterial and antifungal agents against some phyto- and human pathogens and the minimum inhibitory concentration (MIC) data showed that complex (A) has the lowest MIC for Listeria and E. coli (10.8 µg/mL). Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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11 pages, 2168 KiB  
Article
Replacement of the Common Chromium Source CrCl3(thf)3 with Well-Defined [CrCl2(μ-Cl)(thf)2]2
by Dong Geun Lee, Jun Won Baek, Jung Hyun Lee, Hyun Ju Lee, Yeong Hyun Seo, Junseong Lee, Chong Gu Lee and Bun Yeoul Lee
Molecules 2021, 26(4), 1167; https://doi.org/10.3390/molecules26041167 - 22 Feb 2021
Cited by 8 | Viewed by 3918
Abstract
CrCl3(thf)3 is a common starting material in the synthesis of organometallic and coordination compounds of Cr. Deposited as an irregular solid with no possibility of recrystallization, it is not a purity guaranteed chemical, causing problems in some cases. In this [...] Read more.
CrCl3(thf)3 is a common starting material in the synthesis of organometallic and coordination compounds of Cr. Deposited as an irregular solid with no possibility of recrystallization, it is not a purity guaranteed chemical, causing problems in some cases. In this work, we disclose a well-defined form of the THF adduct of CrCl3 ([CrCl2(μ-Cl)(thf)2]2), a crystalline solid, that enables structure determination by X-ray crystallography. The EA data and XRD pattern of the bulk agreed with the revealed structure. Moreover, its preparation procedure is facile: evacuation of CrCl3·6H2O at 100 °C, treatment with 6 equivalents of Me3SiCl in a minimal amount of THF, and crystallization from CH2Cl2. The ethylene tetramerization catalyst [iPrN{P(C6H4-p-Si(nBu)3)2}2CrCl2]+[B(C6F5)4]− prepared using well-defined [CrCl2(μ-Cl)(thf)2]2 as a starting material exhibited a reliably high activity (6600 kg/g-Cr/h; 1-octene selectivity at 40 °C, 75%), while that of the one prepared using the impure CrCl3(thf)3 was inconsistent and relatively low (~3000 kg/g-Cr/h). By using well-defined [CrCl2(μ-Cl)(thf)2]2 as a Cr source, single crystals of [(CH3CN)4CrCl2]+[B(C6F5)4]− and [{Et(Cl)Al(N(iPr)2)2}Cr(μ-Cl)]2 were obtained, allowing structure determination by X-ray crystallography, which had been unsuccessful when the previously known CrCl3(thf)3 was used as the Cr source. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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10 pages, 1753 KiB  
Article
Efficient and Reusable Iron Catalyst to Convert CO2 into Valuable Cyclic Carbonates
by Ana P. C. Ribeiro, Peter Goodrich and Luísa M. D. R. S. Martins
Molecules 2021, 26(4), 1089; https://doi.org/10.3390/molecules26041089 - 19 Feb 2021
Cited by 5 | Viewed by 2420
Abstract
The production of cyclic carbonates from CO2 cycloaddition to epoxides, using the C-scorpionate iron(II) complex [FeCl2{κ3-HC(pz)3}] (pz = 1H-pyrazol-1-yl) as a catalyst, is achieved in excellent yields (up to 98%) in a tailor-made ionic [...] Read more.
The production of cyclic carbonates from CO2 cycloaddition to epoxides, using the C-scorpionate iron(II) complex [FeCl2{κ3-HC(pz)3}] (pz = 1H-pyrazol-1-yl) as a catalyst, is achieved in excellent yields (up to 98%) in a tailor-made ionic liquid (IL) medium under mild conditions (80 °C; 1–8 bar). A favorable synergistic catalytic effect was found in the [FeCl2{κ3-HC(pz)3}]/IL system. Notably, in addition to exhibiting remarkable activity, the catalyst is stable during ten consecutive cycles, the first decrease (11%) on the cyclic carbonate yield being observed during the 11th cycle. The use of C-scorpionate complexes in ionic liquids to afford cyclic carbonates is presented herein for the first time. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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Review

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13 pages, 1677 KiB  
Review
Recent Progress in Homogeneous Catalytic Dehydrogenation of Formic Acid
by Naoya Onishi, Ryoichi Kanega, Hajime Kawanami and Yuichiro Himeda
Molecules 2022, 27(2), 455; https://doi.org/10.3390/molecules27020455 - 11 Jan 2022
Cited by 47 | Viewed by 4323
Abstract
Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage [...] Read more.
Recently, there has been a strong demand for technologies that use hydrogen as an energy carrier, instead of fossil fuels. Hence, new and effective hydrogen storage technologies are attracting increasing attention. Formic acid (FA) is considered an effective liquid chemical for hydrogen storage because it is easier to handle than solid or gaseous materials. This review presents recent advances in research into the development of homogeneous catalysts, primarily focusing on hydrogen generation by FA dehydrogenation. Notably, this review will aid in the development of useful catalysts, thereby accelerating the transition to a hydrogen-based society. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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14 pages, 3060 KiB  
Review
Iridaaromatics via Methoxy(alkenyl)carbeneiridium Complexes
by Maria Talavera and Sandra Bolaño
Molecules 2021, 26(15), 4655; https://doi.org/10.3390/molecules26154655 - 31 Jul 2021
Cited by 9 | Viewed by 2307
Abstract
This review describes the development of a versatile methodology to synthesize polycyclic metallaaromatic hydrocarbons based on iridium, as well as the studies that helped us to determine and understand what is required in order to broaden the scope and the selectivity of the [...] Read more.
This review describes the development of a versatile methodology to synthesize polycyclic metallaaromatic hydrocarbons based on iridium, as well as the studies that helped us to determine and understand what is required in order to broaden the scope and the selectivity of the methodology and stabilize the complexes obtained. This methodology aims to open the door to new materials based on graphene fragments. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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26 pages, 40516 KiB  
Review
1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections
by Edwin C. Constable, Richard M. Hartshorn and Catherine E. Housecroft
Molecules 2021, 26(6), 1584; https://doi.org/10.3390/molecules26061584 - 13 Mar 2021
Cited by 8 | Viewed by 3059
Abstract
1,1′-Biisoquinolines are a class of bidentate nitrogen donor ligands in the heterocyclic diimine family. This review briefly discusses their properties and the key synthetic pathways available and then concentrates upon their coordination behaviour. The ligands are of interest as they exhibit the phenomenon [...] Read more.
1,1′-Biisoquinolines are a class of bidentate nitrogen donor ligands in the heterocyclic diimine family. This review briefly discusses their properties and the key synthetic pathways available and then concentrates upon their coordination behaviour. The ligands are of interest as they exhibit the phenomenon of atropisomerism (hindered rotation about the C1–C1′ bond). A notation for depicting the stereochemistry in coordination compounds containing multiple stereogenic centers is developed. The consequences of the chirality within the ligand on the coordination behaviour is discussed in detail. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Organometallic Chemistry)
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