Synthesis, characterization, redox properties, and representative X-ray structures of four- and five-coordinate copper(II) complexes with polydentate aminopyridine ligands

Rybak‐Akimova, Elena V.; Nazarenko, Alexander Y.; Chen, Lisa S.; Krieger, Paul W.; Herrera, Aida M.; Tarasov, Vladislav V.; Robinson, Paul D.

doi:10.1016/s0020-1693(01)00495-9

Cited by 90 publications

(59 citation statements)

References 73 publications

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“…The crystal structures of manganese(II) and copper(II) with its L¢Me2 included in these binuclear complexes have been reported. 5,7 The pyridine functional group on the complex cation with an ethylene group between two N-pyridine-2-ylmethylamines would have a more rigid geometry than that with the propylene group. 8 The Cu-N4 square-planar geometry of [Cu(ClO4)2(LMe2)] is distorted more than that of N, N¢-bis(pyridine-2-ylmethyl) The complex of an isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LMe2)]ClO4) was prepared.…”

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Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Yokoyama

Yoshise

HASE

et al. 2011

X-ray Structure Analysis Online

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The synthesis, electrochemistry, and reactivities of a complex cation, trans-dioxo-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diamineruthenium(VI)(trans-[Ru(LMe2)O2] 2+ ), have been reported. 1 It can oxidize tetrahydrofuran and aromatic hydrocarbons under mild conditions. Its pyridine functional group increases both the redox potential and the reactivity of the ruthenium oxo oxidant. It is considered that its reactivity would also depend on the geometry of the pyridine functional group on the structure of the complex cation. The redox behaviors of [Cu(LMe2) N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)ethane-1,2-diamine (L¢Me2) and perchlorate ions has been also reported. 6 Only one perchlorate ion in [Cu(ClO4)(L¢Me2)]ClO4 coordinates to the Cu 2+ ion. Each N-methyl group of the [Cu(ClO4)(L¢Me2)]ClO4 is placed at a cis configuration. The crystal structures of manganese(II) and copper(II) with its L¢Me2 included in these binuclear complexes have been reported. 5,7 The pyridine functional group on the complex cation with an ethylene group between two N-pyridine-2-ylmethylamines would have a more rigid geometry than that with the propylene group. 8 The Cu-N4 square-planar geometry of [Cu(ClO4)2(LMe2)] is distorted more than that of N, N¢-bis(pyridine-2-ylmethyl) The complex of an isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LMe2)]ClO4) was prepared. Its crystal structure was determined by X-ray diffractometry. [Cu(NCS)(LMe2)]ClO4 crystallized in a triclinic system, and was characterized thus: P1, a = 9.257(3), b = 9.883(4), c = 11.806(5)Å, a = 89.638(12), b = 81.053(10), g = 88.841(12)˚, Z = 2, V = 1066.7(7)Å 3 . The crystal structure was solved by direct methods and refined by full-matrix least squares on F 2 to final values of R1 = 0.058.

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Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Yokoyama

Yoshise

HASE

et al. 2011

X-ray Structure Analysis Online

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“…[89] These are accompanied by a slight distortion of the equatorial CuÀN bonds and a rather strong in-plane ligand field strength. [63] When the cyclam precursor 1 is immobilized in the solgel matrix through route B and metalated by CuCl 2 (X BCu), a shift of the broad envelope of bands to a higher energy occurs (Figure 2) in the visible region (l max = 740 nm), compared to the silylated precursor complex 1-Cu in solution (l max = 806 nm, e = 199 mol À1 L cm À1 in CH 2 Cl 2 ).…”

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Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Brandès

David

Suspène

et al. 2007

Chemistry A European J

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We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

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“…This spectral pattern is characteristic of distorted trigonal-bipyramidal copper(II) complexes. 12,13 Selected bond lengths and angles for 1 are listed in Table 2. In Table 2, the bond angles in the equatorial plane are distorted from the ideal trigonal angle of 120° with one small angle of 104.2(1)° (N2-Cu-N5) between the Cu-N am bond and the equatorial Cu-N py bond and two large angles of 125.9(2)° (N2-Cu-N3) and 127.2(2)° (N3-Cu-N5) between the Cu-N py bonds.…”

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Crystal Structures and Characterization of Copper(II) Complexes of N,N,N'N'-Tetrakis(2-pyridylmethyl)-1,2-ethanediamine

2004

Bulletin of the Korean Chemical Society

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The structure of [Cu(tpen)](ClO 4 ) 2 (tpen = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethanediamine) has been identified by X-ray crystallography. The copper(II) ion is surrounded by two amine N atoms and three pyridine N atoms of the ligand, making a distorted trigonal-bipyramid. Among the six potential N donor atoms (two amine N and four pyridine N atoms), only one pyridine N atom remains uncoordinated. We examined structural changes on addition of Cl − to [Cu(tpen)] 2+ (1). The addition of Cl − in methanol resulted in the formation of a novel dinuclear copper(II) complex [Cu 2 Cl 2 (tpen)](ClO 4 ) 2 ·H 2 O. The structure of the dinuclear complex was verified by X-ray crystallography. Each copper(II) ion in the dinuclear complex showed a distorted square planar geometry with two pyridine N atoms, one amine N atom and one Cl − ion.

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Synthesis, characterization, redox properties, and representative X-ray structures of four- and five-coordinate copper(II) complexes with polydentate aminopyridine ligands

Cited by 90 publications

References 73 publications

Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Crystal Structures and Characterization of Copper(II) Complexes of N,N,N'N'-Tetrakis(2-pyridylmethyl)-1,2-ethanediamine

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