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Inorganics
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Binuclear Complexes II
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Binuclear Complexes II

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

Deadline for manuscript submissions: closed (31 March 2024) | Viewed by 5710

Special Issue Editor

Prof. Dr. Philippe Schollhammer

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Guest Editor
Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, Université de Bretagne Occidentale, 29238 Brest, France
Interests: inorganic molecular chemistry; coordination; organometallic and bioorganometallic chemistry; biomimetism; bimetallic activation; hydrogenases and nitrogenase models; activation of small molecules; synthesis and reactivity; inorganic and organometallic electrochemistry and electrocatalysts
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Binuclear complexes of transition metals continue to attract increasing interest in the field of coordination and organometallic chemistry. They afford very promising perspectives for homogeneous catalysis, thanks to original bond activation processes which are induced by the cooperativity of two metal centers in close proximity. Over the last several decades, polymetallic active sites of metalloenzymes (hydrogenase, nitrogenase or CO-deshydrogenase, etc.) have inspired the search for Earth-abundant transition metal catalysts for challenging processes such as hydrogen production/uptake, nitrogen fixation or CO2 reduction. The biomimicry of outstanding natural cofactors combining bimetallic and metal–ligand cooperativities, such as the active site of [FeFe]-hydrogenases, has strongly stimulated the development of the chemistry of binuclear systems. Recent advances confirm the high ability for the molecular activation and diversity of dinuclear complexes, which are built either using pre-shaped dinuclear platforms or mono-nuclear building blocks, or else with sophisticated encapsulating and dinucleating non-innocent polydentate ligands.

“Binuclear Complexes II" is the second edition of the Special Issue entitled "Binuclear Complexes", published in 2019 in Inorganics. It aims to cover the various and recent developments in transition metal dinuclear complexes, including their synthesis and characterization, their stoichiometric and catalytic activity towards small-molecule transformations as well as physico-chemical (spectroscopic, electrochemical, etc.) and theoretical aspects concerning the investigation of their operating mechanisms.

Prof. Dr. Philippe Schollhammer
Guest Editor

Manuscript Submission Information

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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. Inorganics 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

  • dinuclear complexes
  • bimetallic activation
  • activation of small molecules
  • synthesis and reactivity
  • catalytic activity
  • mechanism determination
  • structure-reactivity relationship

Related Special Issue

Published Papers (5 papers)

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Research

13 pages, 2523 KiB  
Article
Alkane Elimination Preparation of Heterobimetallic MoAl Tetranuclear and Binuclear Complexes Promoting THF Ring Opening
by Léon Escomel, Erwann Jeanneau, Chloé Thieuleux and Clément Camp
Inorganics 2024, 12(3), 72; https://doi.org/10.3390/inorganics12030072 - 28 Feb 2024
Viewed by 1016
Abstract
We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2] [...] Read more.
We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2]2, (1), featuring a 12-membered C4O4Mo2Al2 ring in which isocarbonyls bridge the Mo and Al centers. The addition of pyridine to this complex successfully results in the dissociation of the dimer into a new discrete binuclear complex, [Cp*Mo(CO)2(µ-CO)Al(Py)(iBu)2], (2). Switching the nature of the Lewis base from pyridine to tetrahydrofuran does not lead to the THF analogue of adduct 2, but rather to a complex reaction where one of the identified products corresponds to a tetranuclear species, [Cp*Mo(CO)3(μ-CH2CH2CH2CH2O)Al(iBu)2]2, (3), featuring two bridging alkoxybutyl fragments originating from the C-O ring opening of THF. Compound 3 adds to the unusual occurrences of THF ring opening by heterobimetallic complexes, which is evocative of masked metal-only frustrated Lewis pair behavior and highlights the high reactivity of these Al/Mo assemblies. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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18 pages, 12159 KiB  
Article
Use of the Asymmetrical Chelating N-Donor 2-Imino-Pyridine as a Redox [Fe4S4] Cubane Surrogate at a Di-Iron Site Related to [FeFe]-Hydrogenases
by Andrea Mele, Federica Arrigoni, Luca De Gioia, Catherine Elleouet, François Y. Pétillon, Philippe Schollhammer and Giuseppe Zampella
Inorganics 2023, 11(12), 463; https://doi.org/10.3390/inorganics11120463 - 29 Nov 2023
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Abstract
Two complexes, related to the active site of [FeFe]-hydrogenases, [Fe2(CO)4(κ2-pma)(µ-bdt)] (1) and [Fe2(CO)4(κ2-pma)(µ-pdt)] (2) (bdt = benzene-1,2-dithiolate, pdt = propane-1,2-dithiolate) featuring [...] Read more.
Two complexes, related to the active site of [FeFe]-hydrogenases, [Fe2(CO)4(κ2-pma)(µ-bdt)] (1) and [Fe2(CO)4(κ2-pma)(µ-pdt)] (2) (bdt = benzene-1,2-dithiolate, pdt = propane-1,2-dithiolate) featuring the diaza chelate ligand trans-N-(2-pyridylmethylene)aniline (pma) were prepared, in order to study the influence of such a redox ligand, potentially non-innocent, on their redox behaviours. Both complexes were synthesized by photolysis in moderate yields, and they were characterized by IR, 1H and 13C{1H} NMR spectroscopies, elemental analyses and X-ray diffraction. Their electrochemical study by cyclic voltammetry, in the presence and in the absence of protons, revealed different behaviours depending on the aliphatic or aromatic nature of the dithiolate bridge. Density functional theory (DFT) calculations showed the role of the pma ligand as an electron reservoir, allowing the rationalization of the proton reduction process of complex 1. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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17 pages, 2452 KiB  
Article
Isocyanide Cycloaddition and Coordination Processes at Trigonal Phosphinidene-Bridged MoRe and MoMn Complexes
by M. Angeles Alvarez, M. Esther García, Daniel García-Vivó, Miguel A. Ruiz and Patricia Vega
Inorganics 2023, 11(9), 364; https://doi.org/10.3390/inorganics11090364 - 07 Sep 2023
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Abstract
Heterometallic phosphinidene complexes are appealing species for the construction of novel organophosphorus ligands thanks to the high reactivity expected from the combination of M-P multiple bonding and the intrinsically different electronic and coordination preferences of the distinct metals. In a preliminary study, we [...] Read more.
Heterometallic phosphinidene complexes are appealing species for the construction of novel organophosphorus ligands thanks to the high reactivity expected from the combination of M-P multiple bonding and the intrinsically different electronic and coordination preferences of the distinct metals. In a preliminary study, we found that the heterobimetallic complex [MoReCp(μ-PMes*)(CO)6] (Mes* = 2,4,6-C6H2tBu3) reacted with CN(p-C6H4OMe) via [2+1]-cycloaddition to form a novel azaphosphallene complex. We have now examined in detail the reactions of the above complex and those of its MoMn analogue with different isocyanides, which turned out to be strongly dependent on experimental conditions and on the size of the substituent at the isocyanide. All the products formed follow from one or several of the following reaction pathways: (i) CO substitution by CNR; (ii) addition of CNR at the group 7 metal centre; and (iii) [2+1] cycloaddition of isocyanide at a Mo=P bond to form azaphosphallene groups, with the former process being dominant in reactions at room temperature and for the Mn system. In contrast, low-temperature reactions of the Re system favoured the addition processes, with the [2+1] cycloaddition at Mo=P bonds only taking place at substrates without metal-metal bonds and when the size of the CNR group does not cause unbearable steric clashes when placed in between the Cp and Mes* groups. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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21 pages, 5074 KiB  
Article
Anion Capture at the Open Core of a Geometrically Flexible Dicopper(II,II) Macrocycle Complex
by Sam H. Brooks, Corey A. Richards, Patrick J. Carroll, Michael R. Gau and Neil C. Tomson
Inorganics 2023, 11(9), 348; https://doi.org/10.3390/inorganics11090348 - 24 Aug 2023
Viewed by 1019
Abstract
Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design [...] Read more.
Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (nPDI2, n = 2, 3). A series of dicopper complexes bound by the nPDI2 ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N3, NO2, OSiMe3, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the nPDI2 macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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14 pages, 2218 KiB  
Article
Adding Diversity to Diiron Aminocarbyne Complexes with Amine Ligands
by Chiara Saviozzi, Sara Stocchetti, Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni and Fabio Marchetti
Inorganics 2023, 11(3), 91; https://doi.org/10.3390/inorganics11030091 - 21 Feb 2023
Cited by 2 | Viewed by 1103
Abstract
The reactions of the diiron aminocarbyne complexes [Fe2Cp2(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF3SO3 (R = Me, 1aNCMe; R = Cy, 1bNCMe), freshly prepared from the tricarbonyl precursors 1a–b, with primary amines containing an additional [...] Read more.
The reactions of the diiron aminocarbyne complexes [Fe2Cp2(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF3SO3 (R = Me, 1aNCMe; R = Cy, 1bNCMe), freshly prepared from the tricarbonyl precursors 1a–b, with primary amines containing an additional function (i.e., alcohol or ether) proceeded with the replacement of the labile acetonitrile ligand and formation of [Fe2Cp2(NH2CH2CH2OR’)(CO)(μ-CO){μ-CN(Me)(R)}]CF3SO3 (R = Me, R’ = H, 2a; R = Cy, R’ = H, 2b; R = Cy, R’ = Me, 2c) in 81–95% yields. The diiron-oxazolidinone conjugate [Fe2Cp2(NH2OX)(CO)(μ-CO){μ-CN(Me)2}]CF3SO3, 3, was prepared from 1a, 3-(2-aminoethyl)-5-phenyloxazolidin-2-one (NH2OX) and Me3NO, and finally isolated in 96% yield. In contrast, the one pot reactions of 1a-b with NHEt2 in the presence of Me3NO gave the unstable [Fe2Cp2(NHEt2)(CO)(μ-CO){μ-CN(Me)(R)}]CF3SO3 (R = Me, 4a; R = Cy, 4b) as unclean products. All diiron complexes were characterized by analytical and spectroscopic techniques; moreover, the behavior of 2a–c and 3 in aqueous media was ascertained. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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