Insights into Metalloenzymes and Bioinspired Complexes for Small Molecule Activation

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Bioinorganic Chemistry".

Deadline for manuscript submissions: 31 August 2026 | Viewed by 1676

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Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, Université de Bretagne Occidentale, 29238 Brest, France
Interests: coordination, organometallic and bioorganometallic chemistry; biomimetism; bimetallic activation; hydrogenase and nitrogenase models; activation of small molecules; synthesis and reactivity
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Special Issue Information

Dear Colleagues,

Small molecule transformations in nature, such as reductions of protons, O2, CO, CO2, and N2, are performed by multicomponent metalloenzymes. Understanding and mimicking the mechanisms of these redox transformations remains challenging and requires the development of the chemistry of model complexes as structural, spectroscopic or functional models. This approach employs molecular engineering to control the availability of coordination sites and electron and proton transfers necessary for activation processes through metal–ligand cooperativities, involving redox and proton relay. This is why, in the context of the development of renewable energy and new environmentally friendly processes, metalloenzymes and their active sites provide a source of inspiration for coordination and organometallic chemists.

This Special Issue, titled "Insights into Metalloenzymes and Bioinspired Complexes for Small Molecule Activation”, will cover recent developments on metalloenzymes and bioinspired molecules, such as their synthesis and characterization and their redox behavior and reactivity for small molecule activation.

This Special Issue is dedicated to Dr. Jean Talarmin, who passed away in April 2025, and who contributed over several decades to our shared understanding of electronic transfer processes in dinuclear systems that model the active sites of [FeFe] hydrogenases and nitrogenases.

Prof. Dr. Philippe Schollhammer
Guest Editor

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Keywords

  • metal transition complexes
  • proton and electron transfer
  • activation of small molecules
  • metal–ligand cooperativities
  • synthesis and reactivity
  • electrochemistry
  • catalytic activity
  • mechanism determination
  • structure–reactivity relationship

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Published Papers (2 papers)

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Research

18 pages, 5539 KB  
Article
Oxidation Path and Protonation of [Fe2(CO)4(µ-edt){κ2-(R2PCH2)2NCH2Fc}] (R = Ph, Cy) Biomimetics of [FeFe]-hydrogenases Incorporating a Proton Relay and a Second Redox Center
by Georgia R. F. Orton, Martin Pižl, Sara Belazregue, Andrew J. Lake, Mark R. J. Elsegood, Jeremy K. Cockcroft, Martin B. Smith, František Hartl and Graeme Hogarth
Inorganics 2026, 14(3), 83; https://doi.org/10.3390/inorganics14030083 - 16 Mar 2026
Viewed by 636
Abstract
While many [FeFe]-hydrogenase biomimetics are effective proton-reduction catalysts, few are active for H2 oxidation, and examples containing both a pendant amine group, able to act as a proton relay, and a second redox center, both essential features of the enzymes, are rare. [...] Read more.
While many [FeFe]-hydrogenase biomimetics are effective proton-reduction catalysts, few are active for H2 oxidation, and examples containing both a pendant amine group, able to act as a proton relay, and a second redox center, both essential features of the enzymes, are rare. Here we report the preparation and oxidation chemistry of two ferrocene-functionalized amino-diphosphines (PCNCP), (CH2PR2)2NCH2Fc (R = Ph (1), Cy (2)), and their ethylenedithiolate (edt) diiron complexes, [Fe2(CO)4(μ-edt){κ2-(R2PCH2)2NCH2Fc}] (R = Ph (3), Cy (4)). Their crystallographic characterization shows that PCNCP occupies an apical–basal position. CV responses are slightly R-dependent, showing for 3 and 4 in three separate oxidative processes assigned to successive one-electron oxidation of the diiron core (quasireversible), appended Fc (reversible), and the amine–diiron moiety (irreversible), as confirmed by IR and UV–Vis spectroelectrochemical studies supported by Density Functional Theory (DFT) and Time-dependent Density Functional Theory (TDDFT) calculations. The first oxidation results in a structural rearrangement of the Fe(PNP)(CO) unit and the formation of a semi-bridging carbonyl. Slow protonation of 3 with HBF4∙Et2O affords the corresponding N-protonated cation in acetone, whilst μ-hydride products dominate for both 3 and 4 in CD2Cl2. A preliminary H2 oxidation study was carried out with 3, and while there was some evidence of activity, it was much lower than reported for alkyl-functionalized PCNPC diiron derivatives. Full article
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11 pages, 1863 KB  
Article
Design and Structural Characterization of Ferrocenyl Bithiophene Thioketone-Based Iron Complexes
by Ibrahim Basma, Hassan Abul-Futouh, Alessia Cinci, Sara J. Abaalkhail, Abdulmajeed Abdullah Alayyaf, Phil Köhler and Wolfgang Weigand
Inorganics 2026, 14(1), 14; https://doi.org/10.3390/inorganics14010014 - 28 Dec 2025
Cited by 1 | Viewed by 681
Abstract
The exceptional catalytic efficiency of [FeFe]-hydrogenases has driven intense efforts to reproduce their structure and function in synthetic models. A key structural feature governing the behavior of synthetic H-cluster analogs lies in the identity of the bridging dithiolato ligands that link the iron [...] Read more.
The exceptional catalytic efficiency of [FeFe]-hydrogenases has driven intense efforts to reproduce their structure and function in synthetic models. A key structural feature governing the behavior of synthetic H-cluster analogs lies in the identity of the bridging dithiolato ligands that link the iron centers. These ligands play a pivotal role in tuning the electron density of the metal core, thereby dictating the complex’s redox characteristics and catalytic reactivity. In this context, we herein describe the synthesis and application of ferrocenyl bithiophene-2,2′-yl thioketone (1) as a proligand for assembling biomimetic models of the [FeFe]-hydrogenase active site. The obtained complexes were thoroughly examined using a suite of analytical methods, including NMR and IR spectroscopy, elemental analysis, and a single-crystal X-ray diffraction, affording comprehensive structural and chemical characterization. Furthermore, their electrochemical behavior toward proton reduction and hydrogen evolution was evaluated via cyclic voltammetry, enabling direct comparison with structurally related analogs. Full article
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