Kinetics and thermodynamics of formation of copper-dioxygen adducts: oxygenation of mononuclear copper(I) complexes containing tripodal tetradentate ligands

Karlin, Kenneth D.; Wei, Ning; Jung, Bernhard; Kaderli, Susan; Niklaus, Pascal A.; Zuberbuehler, Andreas D.

doi:10.1021/ja00074a015

Cited by 209 publications

(250 citation statements)

References 3 publications

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“…5,[17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] Detailed kinetic and thermodynamic studies of copper(I) complexes of tmpa 32 and analogous tetradentate tripodal ligands revealed the stepwise formation of a superoxo plex [{Cu(tmpa)} 2 (O 2 )] 2þ (Cu:O 2 = 2:1). 17 The relative stability of those species has been shown to be dependent on the stereochemical nature of the tripodal ligands. Recently, Schindler et al have reported similar observations for the copper(I) complexes with L H,Bn and L Me,Me ligands given in Scheme 1.…”

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confidence: 99%

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Komiyama¹,

Furutachi²,

Nagatomo³

et al. 2004

Bulletin of the Chemical Society of Japan

127

112

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Oxygenation of copper(I) with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) on the terminal nitrogens has been investigated, whereAll the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/ or trans-("-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness of the terminal nitrogens and the reaction conditions. The reaction of a copper( þ ($0:24 mM) and higher dioxygen concentration (P(O 2 ) = $1 atm), the superoxo species is predominantly formed, whereas at a higher concentration of [Cu(L Me,Bn )] þ ($1 mM) and lower dioxygen concentration (P(O 2 ) = $0:02 atm) the formation of the peroxo species is observed.

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confidence: 99%

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Komiyama¹,

Furutachi²,

Nagatomo³

et al. 2004

Bulletin of the Chemical Society of Japan

127

112

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“…observed from Cu 4 L 4 is comparable to those with moderate to high catecholase activities. [8][9][10][11][12][13][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] It is noticeable that the four copper ions are non-coupled in Cu 4 L 4 whereas most model complexes with high catecholase activities are di-or tri-nuclear copper …”

Section: Resultsmentioning

confidence: 99%

Tetrameric Self-Assembly of a Cu(II) Complex Containing Schiff-Base Ligand and Its Unusually High Catecholase-like Activity

Sarkar¹,

Lee²,

Hong³

et al. 2013

Bulletin of the Korean Chemical Society

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We report a new tetrameric supramolecular Cu(II) complex (Cu 4 L 4 = tetrakis(N,N'-bis(salicylidene)-2,2'-ethylenedianiline)Copper(II)) with a Schiff-base ligand (H 2 L = N,N'-bis (salicylaldimine)-1,2-ethylenediamine) containing two N,O-bidentate chelate groups. Though the copper sites of Cu 4 L 4 are non-coupled, the complex exhibits a unsually high catecholase-like activity (k cat = 935 h −1 ) when the Cu 4 L 4 solution is treated with 3,5-di-tert-butylcatechol (3,5-DTBC) at basic condition in the presence of air. Combined information obtained from UV-VIS and EPR measurements could lead the suggestion of the reaction pathway in which the substrate may bind to Cu(II) ions by anti-anti didentate bridging mode.

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“…The spectra were recorded with the program Kinspec235 [23] [24] to obtain the spectra of the adducts.…”

Section: Experimental Partmentioning

confidence: 99%

Kinetics and Mechanism of the Demetallation of Macrocyclic Nickel(II) Complexes by Cyanide

Siegfried

Kaden

2005

Helvetica Chimica Acta

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Dedicated to Professor AndreÂ E. Merbach on the occasion of his 65th birthdayThe kinetics and the mechanism of the cyanide-induced demetallation of a series of Ni 2 complexes with macrocyclic ligands of different ring size (12-to 14-membered; see 1 ± 4) and steric constraints was studied. Although the rates differ by almost five orders of magnitude when compared to each other under fixed experimental conditions (pH 10.5, [CN À ] 10 À2 m), all reactions proceed through the relatively rapid formation of cyano adducts [Ni(CN) n L] (n 1, 2), which then react with additional CN À or HCN to give the final products. Of paramount importance for the reaction rate is the geometry and configuration of the cyano adducts [Ni(CN) n L] (n 1,2). cis-Dicyano derivatives with a folded macrocycle react faster than trans-compounds. In the case of (1,4,8,11-tetraazacyclotetradecane)2 ), which gives a trans-dicyano adduct, the base-catalyzed N-inversion necessary to obtain the cis-dicyano derivative becomes rate determining at high CN À concentrations.

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Kinetics and thermodynamics of formation of copper-dioxygen adducts: oxygenation of mononuclear copper(I) complexes containing tripodal tetradentate ligands

Cited by 209 publications

References 3 publications

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Tetrameric Self-Assembly of a Cu(II) Complex Containing Schiff-Base Ligand and Its Unusually High Catecholase-like Activity

Kinetics and Mechanism of the Demetallation of Macrocyclic Nickel(II) Complexes by Cyanide

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