- Hemocyanin Models: Synthesis, Structure, and Magnetic Properties of a Binucleating Copper(II) System
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A model compound approach to oxidized hemocyanin is described.The essential features of diamagnetism, 3.6-Angstroem copper-copper separation, approximate tetragonal stereochemistry, imidazole ligation, and bridging groups are reproduced in the azide complex (Cu2(L-Et)(N3))(BF4)2.HL-Et is the septadentate binucleating ligand N,N,N',N'-tetrakis(2-(1-ethylbenzimidazolyl))-2-hydroxy-1,3-diaminopropane prepared in good yield via condensation of 1,2-diaminobenzene with 2-hydroxy-1,3-diaminopropanetetraacetic acid.Related complexes (Cu2(L-Et)X)2+ where X-=OAc-, HCOO-, NO2-, and pyrazolate have quite different magnetic properties.The acetate is ferromagnetic (J ca. +12 1/cm) while the nitrite is antiferromagnetic (J=-139 1/cm).Crystal structures of the weakly coupled acetate complex (Cu2(L-Et)(OAc))(ClO4)2 (monoclinic, P21/n, a=14.190(3) Angstroem, b=22.707(4) Angstroem, c=15.883(4) Angstroem, β=97.20(2) deg, Z=4) and the diamagnetic azide complex (Cu2(L-Et)(N3))(BF4)2 (monoclinic, C2/m, a=19.082(3) Angstroem, b=23.896(3) Angstroem, c=13.230(2) Angstroem, β=116.21(1) deg, Z=4) suggest that these differences have their origin in the orientation of the ? magnetic orbitals with respect to the bridging ligands.The particular mode of 1,3-bridging azide in (Cu2(L-Et)(N3))2+, where it is supported by an alkoxide bridge from L-Et, has not been previously observed.It allows close approach of the copper(II) atoms (3.615(3) Angstroem) and thus becomes aviable stereochemistry for metazidohemocyanin.The present studies support the idea that tetragonally of the copper(II) stereochemistry is important for attaining diamagnetism in oxy- and methemocyanins and that alkoxide from serine or threonine would be well suited to the role of a bridging endogenous ligand.
- McKee, Vickie,Zvagulis, Maruta,Dagdigian, Jeffrey V.,Patch, Marianne G.,Reed, Christopher A.
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- A Mechanistic Study on the Reaction of Non-Heme Diiron(III)-Peroxido Complexes with Benzoyl Chloride
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Dinuclear iron peroxido complexes are important intermediates for selective oxidation reactions. A detailed kinetic study of the reaction of benzoyl chloride (BzCl) with a dinuclear iron non-heme cis end-on peroxido complex with the ligand EtHPTB (N,N,N′,
- Lerch, Markus,Achazi, Andreas J.,Mollenhauer, Doreen,Becker, Jonathan,Schindler, Siegfried
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p. 4122 - 4132
(2021/09/30)
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- POLYDENTATE LIGAND METAL COMPLEX
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The present invention provides a metal complex that has excellent durability, and a device and the like having excellent durability that uses such a metal complex. Specifically, the present invention provides a metal complex comprising (a) a polydentate ligand having denticity of five or more that includes a heteroaromatic ring which contains two or more atoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and (b) an ion of a metal selected from the group consisting of cerium, praseodymium, ytterbium, and lutetium; a composition comprising the metal complex and a charge transport material; an organic thin film obtained by using the metal complex or composition; and a device obtained by using the metal complex, composition, or organic thin film.
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Page/Page column 19
(2012/09/05)
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- MULTINUCLEAR COMPLEX AND CONDENSATION PRODUCT THEREOF
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A multinuclear complex comprising a plurality of metal atoms and a ligand L coordinating to the metal atoms, and satisfying the following conditions (i), (ii), (iii) and (iv): (i) The ligand L has a monovalent group represented by the following general fo
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Page/Page column 13
(2009/03/07)
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- Rapid phosphorus triester hydrolysis catalyzed by bimetallic tetrabenzimidazole complexes
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Bimetallic complexes based on the binucleating ligand N,N,N′, N′-tetrakis[(2-benzimidazolyl)methyl]-2-hydroxy-1,3-diaminopropane ( 1L) and its new toluoyl ester derivative (2L) catalyze the hydrolysis of phosphorus triesters at ambie
- Klinkel, Kortney L.,Kiemele, Lauren A.,Gin, Douglas L.,Hagadorn, John R.
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p. 2919 - 2921
(2008/09/19)
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