Crystal and molecular structure of bis(.mu.-bromo)bis(N,N,N',N'-tetraethylethylenediamine)dicopper(I) and the kinetics of its oxidation by dioxygen in nitrobenzene

Churchill, Melvyn Rowen; Davies, Geoffrey; El-Sayed, Mohamed A.; Fournier, Jay A; Hutchinson, John P.; Zubieta, Jon

doi:10.1021/ic00174a029

Cited by 37 publications

(31 citation statements)

References 2 publications

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“…Inrecent years, crystalstructures of dinuclearCu(I)complexes bridged by halogens and stabilized by N-based ligands have been studied extensively [1][2][3][4]. Wereport here the crystalstructure of a m -bromo-bridged dinuclearc opper(I)c omplex with tert-butyl-(4-methyl-pyridin-2-yl)-amine ligands.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(μ-bromo)-tetrakis(tert-butyl-(4-methylpyridin- 2-yl)-amine)-dicopper(I), Cu2Br2(C10H16N2)4

Glatz¹,

Irrgang²,

Kempe³

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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C 40 H 64 Br 2 Cu 2 N 8 ,monoclinic, C 12/c 1(no. 15), a =11.3890(7) Å, b =16.5070(8) Å, c =23.728(2) Å, Source of materialTwo equivalents of tert-butyl-(4-methyl-pyridin-2-yl)-amine dissolved in THFweretreated with two equivalents of n -butyllithium at0°C.This solutionwasadded to asuspension of one equivalent CuBr 2 in THF.After removalofthe solvent the residue wasextracted twice with hexane and filtered. Colorless crystals suitable for X-rayanalysis were obtained after slow evaporation of the solvent. Experimental detailsWhile the Hatom bonded to the Natom waslocated and refined due to its importance in the hydrogen bonding pattern, the other H atoms were included atcalculated positions. Discussion

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Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(μ-bromo)-tetrakis(tert-butyl-(4-methylpyridin- 2-yl)-amine)-dicopper(I), Cu2Br2(C10H16N2)4

Glatz¹,

Irrgang²,

Kempe³

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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“…Three electrodes were a Beckman Pt working electrode (flat circular sheet, 5 mm diameter) and a Pt wire auxiliary electrode. All potentials were measured with respect to Ag/Ag + (1.0Â 10 )3 M AgNO 3 in 0.1 M tetrabutyl-ammoniumperchlorate (TBAP) in CH 2 Cl 2 ) as a non-aqueous refer- [4] showed that the complex formed from 1 mol of TEED and 1 mol of Cu(I) bromide crystallizes as a bis(l-bromo)-bridged dimer from CH 2 Cl 2 /ether at room temperature. Each Cu(I) atom exhibits a distorted tetrahedral coordination environment.…”

Section: Physical Measurementsmentioning

confidence: 99%

“…For [LCuX] 2 Cat; L = TMED, X = Cl, Br or I, all have a broad band with a long tail, which are characteristic for dimeric distorted five coordinate Cu(II) [4][5][6][7][8][9][10][11][26][27][28][29]. When X changes from Cl to Br or I, absorptivity, M )1 cm )1 , is slightly increased and also the broadening of the band is decreased, Figure 1.…”

Section: Electronic Spectramentioning

confidence: 99%

“…Particular attention has been focused on the reactions of halo(amine)copper(I) complexes with O 2 which are the basis of many useful catalytic systems [4][5][6][7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

“…A systematic kinetic study using a variety of Cu/ amine stoichiometries in aprotic solvents has been carried out [4][5][6][7][8][9][10][11][12]. Aprotic solvents are appropriate because the active sites of Cu containing proteins are hydrophobic [13].…”

Section: Introductionmentioning

confidence: 99%

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Oxidation of bis(µ-halo)-bis[(diamine)copper(I)] complexes [LCuX]2; L = TMED, X = Cl, Br or I, L = TEED or TMPD, X = Cl, with the two electron organo oxidizing agent, tetrachloro-1,2-benzoquinone(TClBQ) in aprotic media: models for intermediates in catalytic catechol oxidase

El-Sayed

Abdel-Hamid

El-Zayat

et al. 2006

Transition Met Chem

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Well structurally characterized bis(l-halo)-bis[(diamine)copper(I)] complexes [LCuX] 2 ; L = TMED, tetramethylethylenediamine, X = Cl, Br or I and L = TEED, tetraethylethylenediamine, or TMPD, tetramethylpropanediamine, X = Cl, react quantitatively with tetrachloro-1,2-benzoquinone (TClBQ) as two electron oxidizing agent in O 2 -free CH 2 Cl 2 or PhNO 2 to form a dimeric [LCuX] 2 Cat (Cat = catechol) as indicated by cryoscopic measurements. Infrared spectra was in agreement with total reduction of TClBQ to the corresponding catechol. Electronic spectra indicated a dimeric distorted five coordinate Cu(II) and EPR spectra suggested a square pyramidal arrangement around the Cu(II) centers in [LCuX] 2 Cat. The ligand field strength for diamine ligand was higher for the five member chelating ring (TMED) relative to the six membered one (TMPD). Electrochemical reduction of Cu centers in [LCuX] 2 Cat were irreversible and occurred at a less negative potential when X = I.

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From Diamines, Triamines and Polyamines

Dilworth¹,

Morton²

1995

Inorganic Reactions and Methods

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Crystal and molecular structure of bis(.mu.-bromo)bis(N,N,N',N'-tetraethylethylenediamine)dicopper(I) and the kinetics of its oxidation by dioxygen in nitrobenzene

Cited by 37 publications

References 2 publications

Crystal structure of bis(μ-bromo)-tetrakis(tert-butyl-(4-methylpyridin- 2-yl)-amine)-dicopper(I), Cu2Br2(C10H16N2)4

Crystal structure of bis(μ-bromo)-tetrakis(tert-butyl-(4-methylpyridin- 2-yl)-amine)-dicopper(I), Cu2Br2(C10H16N2)4

Oxidation of bis(µ-halo)-bis[(diamine)copper(I)] complexes [LCuX]2; L = TMED, X = Cl, Br or I, L = TEED or TMPD, X = Cl, with the two electron organo oxidizing agent, tetrachloro-1,2-benzoquinone(TClBQ) in aprotic media: models for intermediates in catalytic catechol oxidase

From Diamines, Triamines and Polyamines

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