Submit to Molecules Review for Molecules Propose a Special Issue

Journal Browser

► Journal Browser

Recent Advances in the Chemistry of Organoiron Compounds

Print Special Issue Flyer
Special Issue Editors
Special Issue Information
Keywords
Published Papers

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 20409

Share This Special Issue

Special Issue Editor

Prof. Dr. Fabio Marchetti

E-Mail Website
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.

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

Published Papers (6 papers)

Download All Papers

Research

Jump to: Review

21 pages, 9948 KiB

Open AccessArticle

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 2050

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·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)

► Show Figures

Graphical abstract

22 pages, 3516 KiB

Open AccessArticle

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 - 06 Jul 2020

Cited by 8 | Viewed by 3202

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 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 Fe^III 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)

► Show Figures

Figure 1

Review

Jump to: Research

26 pages, 18873 KiB

Open AccessReview

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 - 06 May 2021

Cited by 13 | Viewed by 2986

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 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 Fe^II-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, Fe^III 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)

► Show Figures

Figure 1

29 pages, 5967 KiB

Open AccessReview

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 34 | Viewed by 4426

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 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)

► Show Figures

Graphical abstract

26 pages, 5090 KiB

Open AccessReview

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 8 | Viewed by 4033

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 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)

► Show Figures

Graphical abstract

12 pages, 5244 KiB

Open AccessReview

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 3005

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 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)

► Show Figures