Tetranuclear and Octanuclear Manganese Carboxylate Clusters:  Preparation and Reactivity of (NBun4)[Mn4O2(O2CPh)9(H2O)] and Synthesis of (NBun4)2[Mn8O4(O2CPh)12(Et2mal)2(H2O)2] with a “Linked-Butterfly” Structure

Wemple, Michael W.; Tsai, Hui Lien; Wang, Sheyi; Claude, Juan Pablo; Streib, William E.; Huffman, John C.; Hendrickson, David N.; Christou, George

doi:10.1021/ic9603013

Cited by 126 publications

(71 citation statements)

References 47 publications

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“…Antiferromagnetically coupled manganese clusters in the literature have also shown significant deviation at 300 K from the expected spin-only value. [16][17][18][19][20] …”

Section: Discussionmentioning

confidence: 99%

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

et al. 2013

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The oxygen-evolving complex (OEC) of photosystem II contains a Mn 4 CaO n catalytic site, in which reactivity of bridging oxidos is fundamental to OEC function. We synthesized structurally relevant cuboidal Mn 3 MO n complexes (M = Mn, Ca, Sc; n = 3,4) to enable mechanistic studies of reactivity and incorporation of μ 3 -oxido moieties. We found that Mn IV 3 CaO 4 and Mn IV 3 ScO 4 were unreactive toward trimethylphosphine (PMe 3 ). In contrast, our Mn III 2 Mn IV 2 O 4 cubane reacts with this phosphine within minutes to generate a novel Mn III 4 O 3 partial cubane plus Me 3 PO. We used quantum mechanics to investigate the reaction paths for oxygen atom transfer to phosphine from Mn III 2 Mn IV 2 O 4 and Mn IV 3 CaO 4 . We found that the most favorable reaction path leads to partial detachment of the CH 3 COO − ligand, which is energetically feasible only when Mn(III) is present. Experimentally, the lability of metal-bound acetates is greatest for Mn III 2 Mn IV 2 O 4 . These results indicate that even with a strong oxygen atom acceptor, such as PMe 3 , the oxygen atom transfer chemistry from Mn 3 MO 4 cubanes is controlled by ligand lability, with the Mn IV 3 CaO 4 OEC model being unreactive. The oxidative oxide incorporation into the partial cubane, Mn III 4 O 3 , was observed experimentally upon treatment with water, base, and oxidizing equivalents. 18 O-labeling experiments provided mechanistic insight into the position of incorporation in the partial cubane structure, consistent with mechanisms involving migration of oxide moieties within the cluster but not consistent with selective incorporation at the site available in the starting species. These results support recent proposals for the mechanism of the OEC, involving oxido migration between distinct positions within the cluster.

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“…Antiferromagnetically coupled manganese clusters in the literature have also shown significant deviation at 300 K from the expected spin-only value. [16][17][18][19][20] …”

Section: Discussionmentioning

confidence: 99%

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

et al. 2013

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“…Timedependent DFT calculations were performed on this state, allowing only for transitions to the vacant Mn-1s orbital. The energy scale was recalibrated by shifting the energy axes of calculated absorption and emission transitions by the same value (+167.2 eV) such that the position of the simulated preedge feature of MnO 4 -ion (at Mn K-edge) matched the experimental data.…”

Section: Simulations With Orca (Dft)mentioning

confidence: 99%

“…In Photosystem II (PSII), water is split (oxidized) at a protein-bound Mn 4 Ca(µ-O) n complex. This photosynthetic water oxidation is of outstanding importance for biosphere and atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex–XANES, Kα/Kβ/Kβ-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

Zaharieva

Chernev

Risch

et al. 2009

J. Phys.: Conf. Ser.

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“…These structures have high ground state spins as determined by oxidation state and topology of the polynuclear transition metal core. [8][9][10] ESCA experiments were performed on a Physical Electronics 5400 ESCA system using Mg Kcx radiation (1253.6 eV) and a hemispherical analyzer pass energy of 17.90 eV giving an overall energy resolution of 1.1 eV. All binding energies are referenced to the Fermi level of the analytical instrument as calibrated to the Au 4f peaks.…”

Section: Methodsmentioning

confidence: 99%

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

2001

Self Cite

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Oxo-bridged manganese polynuclear complexes have applications in a variety of technologies, such as single-molecule nanomagnets, catalysis and photosynthetic redox chemistry. The reason that these types of compounds are capable of such important and varied technologies is thought to be because they possess ground states with large spin values. However, the electronic, structural and magnetochemical relationships are not well understood and need to be thoroughly investigated to adequately explain why Mn is such an integral part of so many useful processes. X-ray photoemission spectroscopy was used to study the Mn 3p, 3s and valence band electronic behavior as a function of Mn cluster structural properties, where the cluster size and nuclearity are systematically varied. Results show a chemical shift of the Mn 3 p3/2,1/2 spin-orbit pair related to the cluster size and nuclearity. Also, the Mn 3s 7 S and 5S final state multiplet components shift since it involves the binding energy of a ligand valence electron. In addition, the branching ratio of the 78158 states is related to the 3s 3d electron correlation. Specifically, in the 7S state, the remaining 3s electron is well correlated with 3d electrons of parallel spin, while in the 5S state the two spins are antiparallel. Changes in this electron correlation are clearly observed in the 7 S.S branching ratio as a function of cluster size and ligand electronegativity.

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Tetranuclear and Octanuclear Manganese Carboxylate Clusters: Preparation and Reactivity of (NBuⁿ₄)[Mn₄O₂(O₂CPh)₉(H₂O)] and Synthesis of (NBuⁿ₄)₂[Mn₈O₄(O₂CPh)₁₂(Et₂mal)₂(H₂O)₂] with a “Linked-Butterfly” Structure

Cited by 126 publications

References 47 publications

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex–XANES, Kα/Kβ/Kβ-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

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Tetranuclear and Octanuclear Manganese Carboxylate Clusters: Preparation and Reactivity of (NBun4)[Mn4O2(O2CPh)9(H2O)] and Synthesis of (NBun4)2[Mn8O4(O2CPh)12(Et2mal)2(H2O)2] with a “Linked-Butterfly” Structure

Cited by 126 publications

References 47 publications

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn3MOn Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn3MOn Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex–XANES, Kα/Kβ/Kβ-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

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Tetranuclear and Octanuclear Manganese Carboxylate Clusters: Preparation and Reactivity of (NBuⁿ₄)[Mn₄O₂(O₂CPh)₉(H₂O)] and Synthesis of (NBuⁿ₄)₂[Mn₈O₄(O₂CPh)₁₂(Et₂mal)₂(H₂O)₂] with a “Linked-Butterfly” Structure

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn₃MO_n Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies