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Recent Advances in the Chemistry of Organoiron Compounds

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

Deadline for manuscript submissions: closed (30 June 2021) | Viewed by 21026

Special Issue Editor


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Guest Editor
Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Moruzzi 13, 56124 Pisa, Italy
Interests: coordination chemistry of transition metals; bioorganometallic chemistry; anticancer metal complexes; CO2 activation

Special Issue Information

Dear Colleagues,

Iron is a unique metal element in terms of its availability, cost effectiveness, and low toxicity, and therefore, the advancement in the applications of iron compounds in various fields is highly desirable. In this regard, the serendipitous discovery of ferrocene represented a turning point for modern organometallic chemistry; therefore, a large variety of iron-based organometallic structures has been synthesized and investigated. Thus, organoiron molecular compounds have been intensively studied both in terms of basic research and for their potential uses, including as catalysts for sustainable processes, in view of replacing precious and more toxic metals, the mimetics of natural enzymes, and pharmaceuticals.

This Special Issue will cover all aspects of the synthesis, structural elucidation, theoretical and mechanistic studies, reactivity, properties, and applications of organoiron complexes.

Prof. Fabio Marchetti
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 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.

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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
  • Earth abundant metals
  • Biological activity
  • Catalysis
  • Activation of small molecules
  • Ligand functionalization
  • Theoretical modelling

Published Papers (6 papers)

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Research

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21 pages, 9948 KiB  
Article
Magnetism, Conductivity and Spin-Spin Interactions in Layered Hybrid Structure of Anionic Radicals [Ni(dmit)2] Alternated by Iron(III) Spin-Crossover Complex [Fe(III)(3-OMe-Sal2trien)] and Ferric Moiety Precursors
by Yuri N. Shvachko, Nataliya G. Spitsyna, Denis V. Starichenko, Vladimir N. Zverev, Leokadiya V. Zorina, Sergey V. Simonov, Maksim A. Blagov and Eduard B. Yagubskii
Molecules 2020, 25(21), 4922; https://doi.org/10.3390/molecules25214922 - 24 Oct 2020
Cited by 4 | Viewed by 2148
Abstract
In this study, crystals of the hybrid layered structure, combined with Fe(III) Spin-Crossover (SCO) complexes with metal-dithiolate anionic radicals, and the precursors with nitrate and iodine counterions, are obtained and characterized. [Fe(III)(3-OMe-Sal2trien)][Ni(dmit)2] (1), [Fe(III)(3-OMe-Sal2trien)]NO3 [...] Read more.
In this study, crystals of the hybrid layered structure, combined with Fe(III) Spin-Crossover (SCO) complexes with metal-dithiolate anionic radicals, and the precursors with nitrate and iodine counterions, are obtained and characterized. [Fe(III)(3-OMe-Sal2trien)][Ni(dmit)2] (1), [Fe(III)(3-OMe-Sal2trien)]NO3·H2O (2), [Fe(III)(3-OMe-Sal2trien)]I (3) (3-OMe-Sal2trien = hexadentate N4O2 Schiff base is the product of the condensation of triethylenetetramine with 3-methoxysalicylaldehyde; H2dmit = 2-thioxo-1,3-dithiole-4,5-dithiol). Bulk SCO transition was not achieved in the range 2.0–350 K for all three compounds. Alternatively, the hybrid system (1) exhibited irreversible segregation into the spatial fractions of Low-Spin (LS) and High-Spin (HS) phases of the ferric moiety, induced by thermal cycling. Fractioning was studied using both SQUID and EPR methods. Magnetic properties of the LS and HS phases were analyzed in the framework of cooperative interactions with anionic sublattice: Anion radical layers Ni(dmit)2 (1), and H-bonded chains with NO3 and I (2,3). LS phase of (1) exhibited unusual quasi-two-dimensional conductivity related to the Arrhenius mechanism in the anion radical layers, ρ||c = 2 × 105 Ohm·cm and ρ⊥c = 7 × 102 Ohm·cm at 293 K. Ground spin state of the insulating HS phase was distinctive by ferromagnetically coupled spin pairs of HS Fe3+, S = 5/2, and metal-dithiolate radicals, S = 1/2. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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22 pages, 3516 KiB  
Article
Iron’s Wake: The Performance of Quantum Mechanical-Derived Versus General-Purpose Force Fields Tested on a Luminescent Iron Complex
by Valentin Diez-Cabanes, Giacomo Prampolini, Antonio Francés-Monerris, Antonio Monari and Mariachiara Pastore
Molecules 2020, 25(13), 3084; https://doi.org/10.3390/molecules25133084 - 6 Jul 2020
Cited by 8 | Viewed by 3305
Abstract
Recently synthetized iron complexes have achieved long-lived excited states and stabilities which are comparable, or even superior, to their ruthenium analogues, thus representing an eco-friendly and cheaper alternative to those materials based on rare metals. Most of computational tools which could help unravel [...] Read more.
Recently synthetized iron complexes have achieved long-lived excited states and stabilities which are comparable, or even superior, to their ruthenium analogues, thus representing an eco-friendly and cheaper alternative to those materials based on rare metals. Most of computational tools which could help unravel the origin of this large efficiency rely on ab-initio methods which are not able, however, to capture the nanosecond time scale underlying these photophysical processes and the influence of their realistic environment. Therefore, it exists an urgent need of developing new low-cost, but still accurate enough, computational methodologies capable to deal with the steady-state and transient spectroscopy of transition metal complexes in solution. Following this idea, here we focus on the comparison between general-purpose transferable force-fields (FFs), directly available from existing databases, and specific quantum mechanical derived FFs (QMD-FFs), obtained in this work through the Joyce procedure. We have chosen a recently reported FeIII complex with nanosecond excited-state lifetime as a representative case. Our molecular dynamics (MD) simulations demonstrated that the QMD-FF nicely reproduces the structure and the dynamics of the complex and its chemical environment within the same precision as higher cost QM methods, whereas general-purpose FFs failed in this purpose. Although in this particular case the chemical environment plays a minor role on the photo physics of this system, these results highlight the potential of QMD-FFs to rationalize photophysical phenomena provided an accurate QM method to derive its parameters is chosen. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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Review

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26 pages, 18873 KiB  
Review
Bringing Homogeneous Iron Catalysts on the Heterogeneous Side: Solutions for Immobilization
by Fabio Moccia, Luca Rigamonti, Alessandro Messori, Valerio Zanotti and Rita Mazzoni
Molecules 2021, 26(9), 2728; https://doi.org/10.3390/molecules26092728 - 6 May 2021
Cited by 14 | Viewed by 3090
Abstract
Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in [...] Read more.
Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in homogeneous conditions, while heterogeneous catalysts would be better performing and more desirable systems for a broad industrial application. In this review, approaches for heterogenization of iron catalysts reported in the literature within the last two decades are summarized, and utility and critical points are discussed. The immobilization on silica of bis(arylimine)pyridyl iron complexes, good catalysts in the polymerization of olefins, is the first useful heterogeneous strategy described. Microporous molecular sieves also proved to be good iron catalyst carriers, able to provide confined geometries where olefin polymerization can occur. Same immobilizing supports (e.g., MCM-41 and MCM-48) are suitable for anchoring iron-based catalysts for styrene, cyclohexene and cyclohexane oxidation. Another excellent example is the anchoring to a Merrifield resin of an FeII-anthranilic acid complex, active in the catalytic reaction of urea with alcohols and amines for the synthesis of carbamates and N-substituted ureas, respectively. A SILP (Supported Ionic Liquid Phase) catalytic system has been successfully employed for the heterogenization of a chemoselective iron catalyst active in aldehyde hydrogenation. Finally, FeIII ions supported on polyvinylpyridine grafted chitosan made a useful heterogeneous catalytic system for C–H bond activation. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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29 pages, 5967 KiB  
Review
Recent Advances in Asymmetric Iron Catalysis
by Alessandra Casnati, Matteo Lanzi and Gianpiero Cera
Molecules 2020, 25(17), 3889; https://doi.org/10.3390/molecules25173889 - 26 Aug 2020
Cited by 36 | Viewed by 4567
Abstract
Asymmetric transition-metal catalysis represents a fascinating challenge in the field of organic chemistry research. Since seminal advances in the late 60s, which were finally recognized by the Nobel Prize to Noyori, Sharpless and Knowles in 2001, the scientific community explored several approaches to [...] Read more.
Asymmetric transition-metal catalysis represents a fascinating challenge in the field of organic chemistry research. Since seminal advances in the late 60s, which were finally recognized by the Nobel Prize to Noyori, Sharpless and Knowles in 2001, the scientific community explored several approaches to emulate nature in producing chiral organic molecules. In a scenario that has been for a long time dominated by the use of late-transition metals (TM) catalysts, the use of 3d-TMs and particularly iron has found, recently, a widespread application. Indeed, the low toxicity and the earth-abundancy of iron, along with its chemical versatility, allowed for the development of unprecedented and more sustainable catalytic transformations. While several competent reviews tried to provide a complete picture of the astounding advances achieved in this area, within this review we aimed to survey the latest achievements and new concepts brought in the field of enantioselective iron-catalyzed transformations. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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26 pages, 5090 KiB  
Review
Iron-Catalyzed C–H Functionalizations under Triazole-Assistance
by Matteo Lanzi and Gianpiero Cera
Molecules 2020, 25(8), 1806; https://doi.org/10.3390/molecules25081806 - 15 Apr 2020
Cited by 10 | Viewed by 4139
Abstract
3d transition metals-catalyzed C–H bond functionalizations represent nowadays an important tool in organic synthesis, appearing as the most promising alternative to cross-coupling reactions. Among 3d transition metals, iron found widespread application due to its availability and benign nature, and it was established as [...] Read more.
3d transition metals-catalyzed C–H bond functionalizations represent nowadays an important tool in organic synthesis, appearing as the most promising alternative to cross-coupling reactions. Among 3d transition metals, iron found widespread application due to its availability and benign nature, and it was established as an efficient catalyst in organic synthesis. In this context, the use of ortho-orientating directing groups (DGs) turned out to be necessary for promoting selective iron-catalyzed C–H functionalization reactions. Very recently, triazoles DGs were demonstrated to be more than an excellent alternative to the commonly employed 8-aminoquinoline (AQ) DG, as a result of their modular synthesis as well as the mild reaction conditions applied for their removal. In addition, their tunable geometry and electronics allowed for new unprecedented reactivities in iron-catalyzed C–H activation methodologies that will be summarized within this review. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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12 pages, 5244 KiB  
Review
Ferrocenyl Phosphorhydrazone Dendrimers Synthesis, and Electrochemical and Catalytic Properties
by Cédric-Olivier Turrin, Eric Manoury and Anne-Marie Caminade
Molecules 2020, 25(3), 447; https://doi.org/10.3390/molecules25030447 - 21 Jan 2020
Cited by 9 | Viewed by 3062
Abstract
The discovery of ferrocene is often associated with the rapid growth of organometallic chemistry. Dendrimers are highly branched macromolecules that can be functionalized at will at all levels of their structure. The functionalization of dendrimers with ferrocene derivatives can be carried out easily [...] Read more.
The discovery of ferrocene is often associated with the rapid growth of organometallic chemistry. Dendrimers are highly branched macromolecules that can be functionalized at will at all levels of their structure. The functionalization of dendrimers with ferrocene derivatives can be carried out easily as terminal functions on the surface, but also at the core, or at one or several layers inside the structure. This review will focus on phosphorhydrazone dendrimers functionalized with ferrocene derivatives, on the surface, at the core, at all layers or within a single layer inside the structure. The first part will describe the synthesis; the second part will concern the electrochemical properties; and the last part will give several examples concerning catalysis, with complexes of ferrocenyl phosphines used as terminal functions of dendrimers. Full article
(This article belongs to the Special Issue Recent Advances in the Chemistry of Organoiron Compounds)
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