Dataset Information

CaMn₃ ^IV O₄ Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

ABSTRACT: We report the single crystal XRD and MicroED structure, magnetic susceptibility, and EPR data of a series of CaMn₃ ^IV O₄ and YMn₃ ^IV O₄ complexes as structural and spectroscopic models of the cuboidal subunit of the oxygen-evolving complex (OEC). The effect of changes in heterometal identity, cluster geometry, and bridging oxo protonation on the spin-state structure was investigated. In contrast to previous computational models, we show that the spin ground state of CaMn₃ ^IV O₄ complexes and variants with protonated oxo moieties need not be S=9/2. Desymmetrization of the pseudo-C₃ -symmetric Ca(Y)Mn₃ ^IV O₄ core leads to a lower S=5/2 spin ground state. The magnitude of the magnetic exchange coupling is attenuated upon oxo protonation, and an S=3/2 spin ground state is observed in CaMn₃ ^IV O₃ (OH). Our studies complement the observation that the interconversion between the low-spin and high-spin forms of the S₂ state is pH-dependent, suggesting that the (de)protonation of bridging or terminal oxygen atoms in the OEC may be connected to spin-state changes.

SUBMITTER: Lee HB

PROVIDER: S-EPMC8319083 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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CaMn3IV O4 Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

Lee Heui Beom HB Shiau Angela A AA Marchiori David A DA Oyala Paul H PH Yoo Byung-Kuk BK Kaiser Jens T JT Rees Douglas C DC Britt R David RD Agapie Theodor T

Angewandte Chemie (International ed. in English) 20210701 32

We report the single crystal XRD and MicroED structure, magnetic susceptibility, and EPR data of a series of CaMn3IV O4 and YMn3IV O4 complexes as structural and spectroscopic models of the cuboidal subunit of the oxygen-evolving complex (OEC). The effect of changes in heterometal identity, cluster geometry, and bridging oxo protonation on the spin-state structure was investigated. In contrast to previous computational models, we ...[more]

PMID: 34042234

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Project description:The oxo- and catecholate-bridged UIV/UIV Pacman complex [{(py)UIVOUIV(μ-O2C6H4)(py)}(LA)] A (LA = a macrocyclic "Pacman" ligand; anthracenylene hinge between N4-donor pockets, ethyl substituents on meso-carbon atom of each N4-donor pocket) featuring a bent UIV-O-UIV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H2O or MeOH to afford [{(py)UIV(μ-OH)2UIV(μ-O2C6H4)(py)}(LA)] (1) and [{(py)UIV(μ-OH)(μ-OMe)UIV(μ-O2C6H4)(py)}(LA)] (2), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S8 or 4 equiv. of Se to provide [{(py)UIV(μ-η2:η2-E2)UIV(μ-O2C6H4)(py)}(LA)] (E = S (3), Se (4)) respectively, in which the [E2]2- ion bridges the two UIV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF2 or 2 equiv. of Me3SiCl to provide [{(py)UIV(μ-X)2UIV(μ-O2C6H4)(py)}(LA)] (X = F (5), Cl (6)), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF2 or Me3SiCl in the presence of O(Bcat)2 at room temperature forms [{(py)UIV(μ-X)(μ-OBcat)UIV(μ-O2C6H4)(py)}(LA)] (X = F (5A), Cl (6A)), which upon heating to 80 °C is converted to 5 and 6, respectively. In order to probe the importance of the bent UIV-O-UIV motif in A on the observed reactivity, the bis(boroxido)-UIV/UIV complex, [{(py)(pinBO)UIVOUIV(OBpin)(py)}(LA)] (B), featuring a linear UIV-O-UIV bond angle was treated with H2O and Me3SiCl. Complex B reacts with two equiv. of either H2O or Me3SiCl to provide [{(py)HOUIVOUIVOH(py)}(LA)] (7) and [{(py)ClUIVOUIVCl(py)}(LA)] (8), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal UIV oxidation state is retained in all of the products 1-8, and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear UIV-O-UIV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Dataset Information

CaMn₃ ^IV O₄ Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

Publications

CaMn<sub>3</sub><sup>IV</sup> O<sub>4</sub> Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

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Dataset Information

CaMn3 IV O4 Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

Publications

CaMn<sub>3</sub><sup>IV</sup> O<sub>4</sub> Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

CaMn₃ ^IV O₄ Cubane Models of the Oxygen-Evolving Complex: Spin Ground States S<9/2 and the Effect of Oxo Protonation.