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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 11559

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
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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

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Keywords

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

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Related Special Issue

Published Papers (7 papers)

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Research

16 pages, 2869 KiB  
Article
Arsine, Stibine and Phosphine Derivatives of [Fe2(CO)6(μ-bdt)] (bdt = Benzenedithiolate): Syntheses, Structures and Spectroscopic and Electrocatalytic Studies
by Ahibur Rahaman, Ummey Kulsume, Fakir R. Alam, Matti Haukka, Shishir Ghosh, Graeme Hogarth, Ebbe Nordlander and Shariff E. Kabir
Inorganics 2025, 13(2), 63; https://doi.org/10.3390/inorganics13020063 - 18 Feb 2025
Viewed by 466
Abstract
The reactivity of the benzenedithiolate (bdt)-bridged complex [Fe2(CO)6(µ-bdt)] with arsine, stibine and phosphine ligands has been studied. The new mono- and disubstituted complexes [Fe2(CO)5(EPh3)(µ-bdt)] (E = As, 1; E = Sb 3 [...] Read more.
The reactivity of the benzenedithiolate (bdt)-bridged complex [Fe2(CO)6(µ-bdt)] with arsine, stibine and phosphine ligands has been studied. The new mono- and disubstituted complexes [Fe2(CO)5(EPh3)(µ-bdt)] (E = As, 1; E = Sb 3) and [Fe2(CO)4(EPh3)2(µ-bdt)] (E = As, 2; E = Sb, 4) and the previously reported [Fe2(CO)4(PPh2H)2(µ-bdt)] (5) have been prepared by Me3NO-initiated carbonyl substitution reactions of [Fe2(CO)6(µ-bdt)] with appropriate ligands at 80 °C. Spectroscopic and single-crystal X-ray diffraction studies reveal that in all cases the introduced ligands occupy apical coordination site(s) lying trans to the iron–iron bond. Their electrochemistry has been probed by cyclic voltammetry and selected complexes have been tested as proton reduction catalysts. Monosubstituted complexes 1 and 3 show two irreversible reductions at ca. −1.7 V and −2.0 V, respectively, relative to Fc+/Fc, while the disubstituted complexes 2 and 5 show a single irreversible reduction at ca. −2.2 V and −1.84 V, respectively. Complexes 1, 3 and 5 can catalyse electrocatalytic proton reduction in the presence of either p-toluene sulfonic acid (TsOH) or trifluoroacetic acid (CF3CO2H). Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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21 pages, 4844 KiB  
Article
Cyanide Addition to Diiron and Diruthenium Bis-Cyclopentadienyl Complexes with Bridging Hydrocarbyl Ligands
by Alessia Cinci, Gianluca Ciancaleoni, Stefano Zacchini and Fabio Marchetti
Inorganics 2024, 12(6), 147; https://doi.org/10.3390/inorganics12060147 - 28 May 2024
Viewed by 1242
Abstract
We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = η5 [...] Read more.
We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = η5-C5H5), namely [M2Cp2(CO)2(µ-CO){µ,η1:η2-CH=C=CMe2}]BF4 (1Fe-Ru), [Ru2Cp2(CO)2(µ-CO){µ,η1:η2-C(Ph)=CHPh}]BF4 (2Ru) and [M2Cp2(CO)2(µ-CO){µ-CN(Me)(R)}]CF3SO3 (3Fe-Ru). While the reaction of 1Fe with Bu4NCN resulted in prevalent allenyl deprotonation, preliminary CO-NCMe substitution in 1Ru enabled cyanide addition to both the allenyl ligand (resulting in the formation of a h1:h2-allene derivative, 5A) and the two metal centers (affording 5B1 and 5B2). The mixture of 5B1-2 was rapidly converted into 5A in heptane solution at 100 °C, with 5A being isolated with a total yield of 60%. Following carbonyl-chloride substitution in 2Ru, CN− was incorporated as a terminal ligand upon Cl− displacement, to give the alkenyl complex 6 (84%). The reactivity of 3Fe and 3Ru is strongly influenced by both the metal element, M, and the aminocarbyne substituent, R. Thus, 7aRu was obtained with a 74% yield from cyanide attack on the carbyne in 3aRu (R = Cy, cyclohexyl), whereas the reaction involving the diiron counterpart 3aFe yielded an unclean mixture of the metastable 7aFe and the CO/CN− substitution product 8aFe. The cyano-alkylidene complexes 7aRu (R = Cy) and 7bFe (R = Me) underwent CO loss and carbene to carbyne conversion in isopropanol at 60–80 °C, giving 8aRu (48%) and 8bFe (71%), respectively. The novel compounds 5A, 5B1-2, 6 and 7aRu were characterized by IR and NMR spectroscopy, with the structure of 7aRu further elucidated by single crystal X-ray diffraction analysis. Additionally, the DFT-optimized structures of potential isomers of 5A, 5B1-2 and 6 were calculated. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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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
Cited by 3 | Viewed by 2024
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
Viewed by 1938
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 - 7 Sep 2023
Viewed by 1374
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
Cited by 3 | Viewed by 1713
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 4 | Viewed by 1714
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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