Ubiquity of cubanes in bioinorganic relevant compounds

Bigness, Alec; Vaddypally, Shivaiah; Zdilla, Michael J.; Mendoza-Cortés, José L.

doi:10.1016/j.ccr.2021.214168

Cited by 9 publications

(8 citation statements)

References 621 publications

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“…Within the d ‐based molecular orbital manifold for the Fe−Fe and Fe−S interactions, the highest spin state corresponds to 42 unpaired electrons for [Fe 13 ] 16+ . A sufficiently large orbital splitting resulting in an intermediate spin orbital population in combination with antiferromagnetic interactions with the four W centers [52,53] could bring the spin value of Tp* 4 W 4 Fe 13 S 12 in the range estimated from the magnetization data.…”

Section: Figurementioning

confidence: 99%

“…Assuming an oxidation state for [Et 4 N] 2 [Tp*WFe 3 S 3 (μ 3 -Cl)Cl 3 ] as W(III), [48,49] a similar effective charge is maintained for Tp* 4 W 4 Fe 13 S 12 according to the XANES data, although further studies are needed to conclusively assign the oxidation state. [50,51] [52,53] could bring the spin value of Tp* 4 W 4 Fe 13 S 12 in the range estimated from the magnetization data.…”

mentioning

confidence: 92%

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High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Scott,

Alves Galico,

Bogacz

et al. 2023

Angew Chem Int Ed

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Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12, displaying a Fe13 core with M‐M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S = 13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

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Section: Figurementioning

confidence: 99%

mentioning

confidence: 92%

High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Scott,

Alves Galico,

Bogacz

et al. 2023

Angew Chem Int Ed

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“…[5][6][7] In the first case, interest is focused on the synthesis of structural models of various Mnbased enzymes, with the most important being the [Mn 4 Ca] water-oxidizing complex (WOC) in photosystem II of green plants and cyanobacteria. [8][9][10][11][12][13] In addition, polynuclear Mn-based complexes are of significant interest in the field of molecular magnetism since they often display large ground state spin values and/or single-molecule magnet (SMM) behaviour. [14][15][16] SMMs are discrete molecular species that exhibit slow magnetic relaxation below a characteristic blocking temperature (T B ), arising from purely intramolecular interactions without the need for long-range ordering.…”

Section: Introductionmentioning

confidence: 99%

“…Manganese‐containing coordination compounds have been the subject of investigation for many years owing to their relevance in a wide range of areas, including bioinorganic chemistry [1–4] and molecular magnetism [5–7] . In the first case, interest is focused on the synthesis of structural models of various Mn‐based enzymes, with the most important being the [Mn 4 Ca] water‐oxidizing complex (WOC) in photosystem II of green plants and cyanobacteria [8–13] . In addition, polynuclear Mn‐based complexes are of significant interest in the field of molecular magnetism since they often display large ground state spin values and/or single‐molecule magnet (SMM) behaviour [14–16] .…”

Section: Introductionmentioning

confidence: 99%

Mixed‐Valence Manganese Carboxylate Clusters, {Mn^III₆Mn^II₄}, {Mn^III₇Mn^II₅Na}, and {Mn^III₇Mn^II₅}, Derived from the Combined Use of Di‐2‐pyridyl Ketone with Selected Aliphatic Diols

Skordi,

Alexandropoulos,

Fournet

et al. 2024

Eur J Inorg Chem

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Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2 (1), Na[Mn12O2(OH)3(OMe){(py)2C(O)2}6{(py)2C(OH)(O)}2(MeCO2)2(H2O)10](ClO4)8 (2) and [Mn12O4(OH)2{(py)2CO2}6{(py)2C(OMe)(O)}(MeCO2)3(NO3)3(H2O)(DMF)2](NO3)2 (3) were prepared from the combination of di‐2‐pyridyl ketone, (py)2CO, with the aliphatic diols (1,3‐propanediol (pdH2) or 1,4‐butanediol (1,4‐bdH2)) in Mn carboxylate chemistry. The reported compounds do not include the aliphatic diols employed in this reaction scheme; however, their use is essential for the formation of 1‐3. The crystal structures of 1‐3 are based on multilayer cores which, to our knowledge, are reported for the first time in Mn cluster chemistry. Direct current (dc) magnetic susceptibility studies showed the presence of dominant antiferromagnetic exchange interactions within 1‐3. Alternating current (ac) magnetic susceptibility studies revealed the presence of out‐of‐phase signals below 3.0 K for 2 and 3 indicating the slow relaxation of the magnetization vector, characteristic of single‐molecule magnets; the Ueff value of 2 was found to be 23 K and the preexponential factor τ0 ~ 7.6 × 10–9 s.

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“…Tetrametallic tetrachalcogenide heterocubane clusters (M4E4, E = O, S) are important reaction centers that effectively mediate proton-coupled, multi-electron chemical processes in biological systems. [1][2][3][4] Prominent examples include [Fe4S4] iron sulfur clusters that are essential electron-transfer cofactors for a range of enzymes. [5][6][7] The CaMn4O4 cluster known as the oxygen evolving complex (OEC, Figure 1a) of Photosystem II, and the NiFe4S4 active site of carbon monoxide dehydrogenase (CODH) are structurally similar heterocubane complexes that play an important role in enzymatic catalysis.…”

Section: Introductionmentioning

confidence: 99%

Metal-Metal Redox Exchange to Produce Heterometallic Manga-nese-Cobalt Oxo Cubanes via a “Dangler” Intermediate

Wheeler,

Tilley

2024

Preprint

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Pendent metals bound to heterocubanes are key components of well-known active sites in enzymes that mediate difficult chemical transformations. Investigations into the specific role of these metal ions, sometimes referred to as "danglers," have been hindered by a paucity of rational synthetic routes to appropriate model structures. To generate pendent metal ions bonded to an oxo cubane through a carboxylate bridge, the cubane Co4(μ3-O)4(OAc)4(t-Bupy)4 (OAc = acetate, t-Bupy = 4-tert-butylpyridine) was exposed to various metal acetate complexes. Reaction with Cu(OAc)2 gave the structur-ally characterized (by X-ray diffraction) dicopper dangler Cu2Co4(μ4-O)2(μ3-O)2(OAc)6(Cl)2(t-Bupy)4. In contrast, the anal-ogous reaction with Mn(OAc)2 produced the MnIV-containing cubane cation [MnCo3(μ3-O)4(OAc)4(t-Bupy)4]+ by way of a metal-metal exchange that gives Co(OAc)2 and [CoIII(μ-OH)(OAc)]n oligomers as byproducts. Additionally, reaction of the formally CoIV cubane complex [Co4(μ3-O)4(OAc)4(t-Bupy)4][PF6] with Mn(OAc)2 gave the corresponding Mn-containing cubane in 80% yield. A kinetic and mechanistic examination of the related metal-metal exchange reaction between Co4(μ3-O)4(OBz)4(py)4 (OBz = benzoate) and [Mn(acac)2(py)2][PF6] by UV-vis spectroscopy provided support for a pro-cess involving rate-determining association of the reactants and electron transfer through a μ-oxo bridge in the adduct intermediate. The rates of exchange correlate with the donor strength of the cubane pyridine and benzoate ligand sub-stituents; more electron-donating pyridine ligands accelerate metal-metal exchange, while both electron donating and withdrawing benzoate ligands can accelerate exchange. These experiments suggest that the basicity of the cubane oxo ligands promotes metal-metal exchange reactivity. The redox potentials of the Mn and cubane starting materials, and isotopic labeling studies, suggest an inner-sphere electron transfer mechanism in a dangler intermediate.

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Ubiquity of cubanes in bioinorganic relevant compounds

Cited by 9 publications

References 621 publications

High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Mixed‐Valence Manganese Carboxylate Clusters, {Mn^III₆Mn^II₄}, {Mn^III₇Mn^II₅Na}, and {Mn^III₇Mn^II₅}, Derived from the Combined Use of Di‐2‐pyridyl Ketone with Selected Aliphatic Diols

Metal-Metal Redox Exchange to Produce Heterometallic Manga-nese-Cobalt Oxo Cubanes via a “Dangler” Intermediate

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Ubiquity of cubanes in bioinorganic relevant compounds

Cited by 9 publications

References 621 publications

High‐Spin and Reactive Fe13 Cluster with Exposed Metal Sites

High‐Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Mixed‐Valence Manganese Carboxylate Clusters, {MnIII6MnII4}, {MnIII7MnII5Na}, and {MnIII7MnII5}, Derived from the Combined Use of Di‐2‐pyridyl Ketone with Selected Aliphatic Diols

Metal-Metal Redox Exchange to Produce Heterometallic Manga-nese-Cobalt Oxo Cubanes via a “Dangler” Intermediate

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High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Mixed‐Valence Manganese Carboxylate Clusters, {Mn^III₆Mn^II₄}, {Mn^III₇Mn^II₅Na}, and {Mn^III₇Mn^II₅}, Derived from the Combined Use of Di‐2‐pyridyl Ketone with Selected Aliphatic Diols