0000000000429951
AUTHOR
Serhiy Demeshko
Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.
Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L1) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L2), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [FeII(CH3CN)(L)]2+ (L = L1 (1); L2 (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [FeIV(O)(L)]2+ (L = L1 (3); L2 (4)), which were characterized by UV–vis spe…
Iron (II) isothiocyanate complexes with substituted pyrazines: Experimental and theoretical views on their electronic structure
Abstract Synthesis, structural, magnetic, Mossbauer and thermal studies of isothiocyanate iron (II) complexes with substituted pyrazines (iodo-, bromo- and amino-derivatives) are discussed here. Complexes with iodo- and bromo-derivatives were found to have the composition [Fe(Ipz)2(SCN)2(H2O)2]·2Ipz (1) and [Fe(Brpz)2(SCN)2(H2O)2]·2Brpz (2), whereas in the case of amino-functionalized pyrazine the formation of [Fe(NH2pz)4(SCN)2] (3) was observed. 3D organization of the molecular complexes is stabilized within different hydrogen, halogen and lone pair–π interactions. Spin state of iron (II) ions in 1–3 was determined as high spin by Mossbauer and magnetic measurements. DFT calculations for t…
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
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 1418388: Experimental Crystal Structure Determination
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CCDC 1033835: Experimental Crystal Structure Determination
Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564
CCDC 1874714: Experimental Crystal Structure Determination
Related Article: Biswanath Das, Afnan Al-Hunaiti, Brenda N. S��nchez-Egu��a, Erica Zeglio, Serhiy Demeshko, Sebastian Dechert, Steffen Braunger, Matti Haukka, Timo Repo, Ivan Castillo, Ebbe Nordlander|2019|Frontiers in Chemistry|7|97|doi:10.3389/fchem.2019.00097
CCDC 1403038: Experimental Crystal Structure Determination
Related Article: Biswanath Das, Afnan Al-Hunaiti, Matti Haukka, Serhiy Demeshko, Steffen Meyer, Albert A. Shteinman, Franc Meyer, Timo Repo, Ebbe Nordlander|2015|Eur.J.Inorg.Chem.||3590|doi:10.1002/ejic.201500576
CCDC 966406: Experimental Crystal Structure Determination
Related Article: Biswanath Das, Bao-Lin Lee, Erik A. Karlsson, Torbjörn Åkermark, Andrey Shatskiy, Serhiy Demeshko, Rong-Zhen Liao, Tanja M. Laine, Matti Haukka, Erica Zeglio, Ahmed F. Abdel-Magied, Per E. M. Siegbahn, Franc Meyer, Markus D. Kärkäs, Eric V. Johnston, Ebbe Nordlander, Björn Åkermark|2016|Dalton Trans.|45|13289|doi:10.1039/C6DT01554A
CCDC 1874712: Experimental Crystal Structure Determination
Related Article: Biswanath Das, Afnan Al-Hunaiti, Brenda N. S��nchez-Egu��a, Erica Zeglio, Serhiy Demeshko, Sebastian Dechert, Steffen Braunger, Matti Haukka, Timo Repo, Ivan Castillo, Ebbe Nordlander|2019|Frontiers in Chemistry|7|97|doi:10.3389/fchem.2019.00097
CCDC 994961: Experimental Crystal Structure Determination
Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564