Catalytic Oxidation of Alkanes and Alkenes by H 2 O 2 with a μ‐Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor
A new mu-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3-[(3-{[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl)(pyridin2-ylmethyl)amino] propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2), has been synthesized and characterized. The ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH3COOH/H2O2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation (TOF = 33 h(-1)) and good activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees…
Water oxidation catalyzed by molecular di- and nonanuclear Fe complexes: importance of a proper ligand framework.
The synthesis of two molecular iron complexes, a dinuclear iron(III,III) complex and a nonanuclear iron complex, based on the di-nucleating ligand 2,2-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)(3)](3+). Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council [621-2013-4872]; Carl Trygger Foundation; DFG (Metal Sites in Biomolecules: Structures, Regulation and Mechanisms) [IRTG 1422]; Swedish Energy Agency
(μ-Acetato-κ2 O:O′)[μ-2,6-bis({bis[(pyridin-2-yl-κN)methyl]amino-κN}methyl)-4-methylphenolato-κ2 O:O](methanol-κO)dizinc bis(perchlorate)
The binuclear title complex, [Zn2(C33H33N6O)(CH3COO2)(CH3OH)](ClO4)2, was synthesized by the reaction between 2,6-bis({[bis(pyridin-2-yl)methyl]amino}methyl)-4-methylphenol (H-BPMP), Zn(OAc)2and NaClO4. The two ZnIIions are bridged by the phenolate O atom of the octadentate ligand and the acetate group. An additional methanol ligand is terminally coordinated to one of the ZnIIions, rendering the whole structure unsymmetric. Other symmetric dizinc complexes of BPMP have been reported. However, to the best of our knowledge, the present structure, in which the two ZnIIions are distinguishable by the number of coordinating ligands and the coordination geometries (octahedral and square-pyramidal…
Di- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand: Catalyst Precursors for Alkene Oxidations
The new di- and tetranuclear Fe(III) μ-oxido complexes [Fe 4 (μ-O) 4 (PTEBIA) 4 ](CF 3 SO 3 ) 4 (CH 3 CN) 2 ] (1a), [Fe 2 (μ-O)Cl 2 (PTEBIA) 2 ](CF 3 SO 3 ) 2 (1b), and [Fe 2 (μ-O)(HCOO) 2 (PTEBIA) 2 ](ClO 4 ) 2 (MeOH) (2) were prepared from the sulfur-containing ligand (2-((2,4-dimethylphenyl)thio)-N,N-bis ((1-methyl-benzimidazol-2-yl)methyl)ethanamine (PTEBIA). The tetrairon complex 1a features four μ-oxido bridges, while in dinuclear 1b, the sulfur moiety of the ligand occupies one of the six coordination sites of each Fe(III) ion with a long Fe-S distance of 2.814(6) A. In 2, two Fe(III) centers are bridged by one oxido and two formate units, the latter likely formed by methanol oxidati…
CCDC 1874713: Experimental Crystal Structure Determination
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CCDC 1874714: Experimental Crystal Structure Determination
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CCDC 1403038: Experimental Crystal Structure Determination
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CCDC 966406: Experimental Crystal Structure Determination
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CCDC 1874712: Experimental Crystal Structure Determination
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