Preparation and Structures of K3[VIII(ox)2(<i>μ</i>-SO4)] and K5[VIII(ox)2(SO4)2]

Kanamori, Kan; Kunita, Noriko; Okamoto, Ken‐ichi; Hidaka, Jinsai

doi:10.1246/bcsj.66.2574

Cited by 9 publications

(7 citation statements)

References 9 publications

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“…24, 64, 65 Thus, the pre-edge features close to the rising-edge energy can be unambiguously related to the direct radicalization effect of the paramagnetic transition metal center.…”

Section: Resultsmentioning

confidence: 95%

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

et al. 2017

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Sulfur K-edge XAS spectra of the monodentate sulfate complexes [MII(itao)(SO4)(H2O)0,1] and [Cu(Me6tren)(SO4)] exhibit well-defined pre-edge transitions at 2479.4 eV, 2479.9 eV, 2478.4 eV, and 2477.7 eV, respectively (M = Co, Ni, Cu), despite having no direct metal-sulfur bond, while the XAS pre-edge of [Zn(itao)(SO4)] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO4)] but not of [Cu(Me6tren)(SO4)] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Pre-edge transitions also appear in the sulfur K-edge XAS of crystalline [MII(SO4)(H2O)] (M = Fe, Co, Ni, Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin-orbitals of the sulfate ligand, inducing negative spin density at sulfate sulfur. Ground state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand anti-bonding orbitals, producing measureable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS pre-edge features 0.5 to 2 eV below the sulfur rising K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the Cu(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the S and the electron hole provides a new mechanism for the counter-intuitive appearance of pre-edge transitions in the XAS spectra of transition metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from Cu(II), which extends across an H-bond bridge between sulfate and the itao ligand and involves orbitals at energies below the frontier set. This electronic structure feature provides direct spectroscopic confirmation of the through-bond electron transfer mechanism of redox-active metalloproteins.

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“…24, 64, 65 Thus, the pre-edge features close to the rising-edge energy can be unambiguously related to the direct radicalization effect of the paramagnetic transition metal center.…”

Section: Resultsmentioning

confidence: 95%

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

et al. 2017

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“…A coordination polymer of sulfate-bridged dioxalatovanadate(III), trans-K 3 [V(ox) 2 -(SO 4 )] n , (121) was structurally characterized in contrast to a monomeric complex trans-K 5 [V(ox) 2 (SO 4 ) 2 ] that was only characterized by IR and Raman spectroscopy. 608 Using the N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine ligand, (tpen), a hexacoordinate V(III)-complex with a bidentate sulfate group was isolated (116) and was found to be stable in aqueous solution. 601 If N,N′-bis(2-pyridylmethyl)-ethylenediamine, (bispicen), was used instead, a dimeric, heptacoordinate V(III)-complex with a bridging sulfate was isolated (127).…”

Section: Vanadium Sulfate Complexesmentioning

confidence: 99%

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

et al. 2004

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“…20 However, the studies of V(III) complexes were obviously less than that of V(IV) or V(V) complexes reported and metal centre of concerning V(III) complexes was six-coordinate mode, while studies on V(III) complexes with seven-coordinate were relatively rare. [21][22][23][24][25][26][27] Although our group has a long-standing interest in the investigation of vanadium complexes with poly(pyrazolyl)borate ligands, 28 Schiff-base ligands 29 and dicarboxylic acid ligands, 30 in order to further extend the structural variety and investigate the relationship between structure and function of the vanadium complexes, here, we firstly designed and synthesized two novel sevencoordinate vanadium(III) complexes with rigid polycarboxylate as ligands, V(dipic 2), and studied the catalytic properties in the aspect of aryl-bound bromosubstituent and oxidation of cyclohexane. It was rather surprising that high catalytic efficiency with total turnover number (TON) value of 395 was reached in the cyclohexane oxidation under mild conditions, which is much higher than the TON values (19, 167 or 308) which have been reported in previous reports.…”

Section: Introductionmentioning

confidence: 99%

Novel vanadium(iii) complexes with rigid phenylpolycarboxylate ligands: synthesis, structures and application in C–H bond activation

et al. 2013

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Two novel vanadium(III) complexes: V(dipic)(Hbdc)(H2O)2 (1) and [V2(dipic)2(H2btec)(H2O)4]·2H2O (2) (H2dipic = 2,6-pyridinedicarboxylic acid, H2bdc = 1,3-benzene-dicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid) are synthesized by the reaction of V2(SO4)3, 2,6-pyridinedicarboxylic acid and 1,3-benzene-dicarboxylic acid (for 1) or 1,2,4,5-benzenetetracarboxylic acid (for 2) under hydrothermal condition at 120 °C for 3 days. They were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction analysis and thermogravimetric analyses (TG). Structural analyses show that the vanadium atoms in the complexes 1 and 2 are both in a pentagonal-bipyramidal coordination environment with the NO6 donor set, and there is intermolecular hydrogen bonding in each complex. Research results found that the complexes exhibited bromination catalytic activity in the single-pot reaction of the conversion of phenol red to bromophenol blue in the mixed solution of H2O-DMF at the constant temperature of 30 ± 0.5 °C with pH = 5.8, and catalytic C-H bond cleavage activity for the peroxidative oxidation (with hydrogen peroxide) of cyclohexane to cyclohexanol and cyclohexanone (the maximum total turnover number is 395) under the mild conditions.

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Preparation and Structures of K3[VIII(ox)2(μ-SO4)] and K5[VIII(ox)2(SO4)2]

Cited by 9 publications

References 9 publications

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

Novel vanadium(iii) complexes with rigid phenylpolycarboxylate ligands: synthesis, structures and application in C–H bond activation

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