Oxidation of copper(II) hydroxyporphyrin (oxophlorin); oxidative ring opening and formation of an ester-linked, dinuclear copper complex

2001 ◽  
Vol 79 (5-6) ◽  
pp. 922-929 ◽  
Author(s):  
Shane Phillips ◽  
Bruce C Noll ◽  
Marilyn M Olmstead ◽  
Alan L Balch
Keyword(s):  
Crystal Structure ◽  
Copper Complex ◽  
Epr Spectroscopy ◽  
Ring Opening ◽  
Oxidative Cleavage ◽  
Dinuclear Complex ◽  
Dinuclear Copper ◽  
Ring Opening Reaction ◽  
Copper Porphyrin ◽  
Ester Linkage

Addition of copper(II) acetate to octaethyl(meso-hydroxy)porphyrin (H2OEPOH) in THF under a dinitrogen atmosphere produces CuII(OEPOH), which has been isolated as red crystals and shown to have a meso-hydroxyporphyrin structure by UV-vis and EPR spectroscopy. CuII(OEPOH) undergoes oxidation by dioxygen to form a novel dinuclear copper complex {CuII(OEPOC(O)OEB)CuII}. This dinuclear complex is composed of a copper(II) meso-substituted porphyrin portion (with a planar CuN4 unit), which is attached through an ester linkage to a helical copper(II) tetrapyrrole that has been ring-opened through oxidative cleavage of a second molecule of CuII(OEPOH). The oxidative ring-opening reaction resembles that of natural heme catabolism but is arrested at a stage where the oxidized meso-carbon is still appended to the helical open tetrapyrrole. A mechanism is suggested for this process.Key words: copper porphyrin, crystal structure, porphyrin oxidation, linear tetrapyrrole, hydroxy-porphyrin, oxophlorin.

scholarly journals 4- and 5-Coordinate Dinuclear Copper(II) Complexes with the Tetraacetylethanediide and an N-Alkylated Diamine or a Triamine

1995 ◽  
Vol 50 (4) ◽  
pp. 536-544 ◽  
Author(s):  
Hide Kambayashi ◽  
Junko Yuzurihara ◽  
Yuichi Masuda ◽  
Hiroko Nakagawa ◽  
Wolfgang Linert ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Esr Spectra ◽  
Crystal Structure Analysis ◽  
Dinuclear Complex ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Dinuclear Copper ◽  
X Ray ◽  
Final Agreement

Six dinuclear copper(II) complexes have been prepared, Cu2(taet)(plam)2X2 where taet = 1,1,2,2-tetraacetylethanediide, plam = N-alkylated polyamine such as tmen = N,N,N′,N′-tetramethylethylenediamine or pmdt = N,N,N′,N′,N′-pentamethyldiethylenetriamine, X = a monovalent anion such as ClO4- , NO3- or Cl-. These complexes are classified into two categories from the results of electronic spectra, IR spectra, and X-ray single crystal structure analysis as follows: (1) 4-coordinate-4-coordinate dinuclear, [Cu2(taet)(tmen)2]X2 (where X = ClO4- or NO3-), (2) 5-coordinate-5-coordinate dinuclear, [Cu2(taet)(tmen)2Cl2], and [Cu2(taet)(pmdt)2]X2 (where X = ClO4-, NO3- , or Cl- ). The crystal structure of Cu2(taet)(tmen)2(ClO4)2 · H2O (1) has been determined by the single crystal X-ray diffraction technique; monoclinic space group P21/a with a = 26.478(3), b = 8.744(1), c = 15.601(3) Å, β = 106.195(9)°, and V = 3468.9(8) Å3 for Z = 4. The final agreement factors are R = 0.097 ( Rw = 0.099). The geometry of each Cu(II) moiety in the dinuclear cation (1) is 4-coordinate square planar with a N2O2 donor set. This tmen-dinuclear complex exhibits a very weak C u (II)-Cu (II) interaction (J = -0.5 cm-1), and shows characteristic ESR spectra with seven hyperfine peaks in 1,2-dichloroethane solution at room temperature. This is not found for the corresponding pmdt-dinuclear complex. All complexes obtained in this study are very soluble in many organic solvents. The tmen-dinuclear complexes show pronounced solvatochromic behavior-dependent on the solvent donor properties. This is not found for the corresponding pmdt-dinuclears, which are stable as 5-coordinated species.

Crystal structure of racemic trans-2-(4-methylphenyl)-cyclohexanol

1994 ◽  
Vol 209 (10) ◽  
Author(s):  
K. Peters ◽  
E.-M. Peters ◽  
H. G. von Schnering ◽  
G. Bringmann ◽  
D. Leimkötter ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Title Compound ◽  
Ring Opening ◽  
Magnesium Bromide ◽  
Cyclohexene Oxide ◽  
Space Group ◽  
Triclinic System ◽  
Ring Opening Reaction

AbstractThe title compound was obtained by a copper-assisted ring opening reaction of cyclohexene oxide using 4-methylphenyl-magnesium-bromide. It crystallizes from n-pentane in the triclinic system, space group

[μ-10,21-Difluoro-3,6,14,17-tetrazatricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21-decaene-23,24-diolato-κ4 N 3,N 6,O 23,O 24:κ4 N 14,N 17,O 23,O 24]bis[methanolcopper(II)] bis(perchlorate)

2007 ◽  
Vol 63 (11) ◽  
pp. m2641-m2641 ◽  
Author(s):  
Jun-Lin Bai ◽  
Hong Zhou ◽  
Zhi-Quan Pan ◽  
Xiang-Gao Meng
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Copper Complex ◽  
Title Complex ◽  
Tetrahedral Geometry ◽  
Intramolecular Hydrogen Bonds ◽  
Dinuclear Copper ◽  
Distorted Tetrahedral Geometry ◽  
O 24 ◽  
Intramolecular Hydrogen

The title complex, [Cu2(C20H16F2N4O2)(CH4O)2](ClO4)2, was synthesized by cyclo-condensation between ethylenediamine and 2,6-diformyl-4-fluorophenol in the presence of CuII ions. This dinuclear copper complex is centrosymmetric. Both Cu atoms are in a distorted tetrahedral geometry, coordinated by three O atoms and two N atoms. The two Cu atoms are bridged by two endogenous phenol O atoms, with a Cu...Cu distance of 2.8998 (7) Å. In the crystal structure, the perchlorate ions link the macrocycles through inter- and intramolecular hydrogen bonds.

Anti-Inflammatory Dinuclear Copper(II) Complexes with Indomethacin. Synthesis, Magnetism and EPR Spectroscopy. Crystal Structure of theN,N-Dimethylformamide Adduct

1999 ◽  
Vol 38 (8) ◽  
pp. 1736-1744 ◽  
Author(s):  
Jane E. Weder ◽  
Trevor W. Hambley ◽  
Brendan J. Kennedy ◽  
Peter A. Lay ◽  
Dugald MacLachlan ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Epr Spectroscopy ◽  
Dinuclear Copper ◽  
Anti Inflammatory
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