Homogeneous oxidative coupling catalysts. Properties of the oxidative coupling initiator obtained from the reaction of copper(I) chloride with oxygen in pyridine

Bodek, Itamar; Davies, Geoffrey

doi:10.1021/ic50185a023

Cited by 36 publications

(14 citation statements)

References 4 publications

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“…electronic spectra exhibit broad intense split maxima in the 750-875 nm, range with molecular absorptivity varying from 600 to 920 M )1 cm )1 . Similar electronic spectra have been obtained for [N n CuX] 4 YY¢, N = Py [22], DENC [24] and Pip [25,26], Y = Y¢ = O, Y = Y¢ = CO 3 , Y = Y¢ = Cat, Y = O, Y¢ = Cat, n = 1 or 2, X = Cl, Br or I. The observed bands are attributed to charge-transfer between a minimum of three halide ligands and copper(II).…”

Section: Resultssupporting

confidence: 76%

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Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Elsayed

Abdel-Salam

El-Zayat

et al. 2005

Transition Met Chem

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This paper describes the synthesis and characterization of heteropolynuclear redox active materials [FerCuCl] 4 YY¢, Y = Y¢ = O, Y = Y¢ = Cat and Y = O, Y¢ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4, 5,6-tetrachlorocatecholato ligand. Manometric O 2 uptake measurements in PhNO 2 show that tetranuclear [FerCuCl] 4 and [FerCuCl] 4 Cat give the tetranuclear oxocopper(II) products [FerCuCl] 4 O 2 and [FerCuCl] 4 CatO, respectively. The absence of carbonyl stretching vibrational bands in [FerCuCl] 4 Cat 2 and [FerCuCl] 4 CatO suggest that tetrachloro-1,2-benzoquinone (TClBQ) is reduced to the corresponding catecholete during the oxidation of copper(I) centers in [FerCuCl] 4 . The near i.r. electronic spectra for [FerCuCl] 4 O 2 , [FerCuCl] 4 CatO and [FerCuCl] 4 Cat 2 exhibit broad intense split maxima in the 750-875 nm range, attributed to a minimum of three halide ligands per Cu. Room temperature solid state e.p.r. spectra for [FerCuCl] 4 CatO and [FerCuCl] 4 Cat 2 are of the axial type, suggesting a square pyramidal geometry around Cu II .

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Section: Resultssupporting

confidence: 76%

“…This is as expected, since the dichloro-bridged dimer [{Cu(Fer)Cl} 2 ] would contain three coordinate metal centers, which are rare for copper(I) complexes [23]. Other hard amine ligands such as pyridine (py) [22], N,N-diethylnicotinamide (DENC) [24] or piperidine (Pip) [25] form tetramers with copper(I) halides under similar conditions.…”

Section: Resultssupporting

confidence: 64%

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Elsayed

Abdel-Salam

El-Zayat

et al. 2005

Transition Met Chem

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“…[22][23][24][25][26][27] Die Oxygenierungsreaktion wurde mithilfe von kryoskopischen Untersuchungen und Sauerstoffaufnahme-Experimenten sowie mithilfe der UV/Vis-, EPR-und IR-Spektroskopie untersucht. Die Studien von Churchill, Davies und Mitarbeitern zeigten, dass sich je nach der Natur des eingesetzten Liganden zwei verschiedene kubusartige Cluster bildeten (Schema 1).…”

Section: Molekulare Cu 2 O-komplexeunclassified

“…Darin liegen die Kupferionen entweder in einem m 2 -oder in einem m 4 -Modus oxo-verbrückt vor. [22][23][24][25][26][27] Die Oxygenierungsreaktion wurde mithilfe von kryoskopischen Untersuchungen und Sauerstoffaufnahme-Experimenten sowie mithilfe der UV/Vis-, EPR-und IR-Spektroskopie untersucht. Zudem wurde festgestellt, dass sich die Komplexe mit m-Oxoliganden von den m 4 -Oxoverbindungen sowohl in ihrer Stabilität als auch in ihrer Reaktivität unterschieden.…”

Section: Molekulare Cu 2 O-komplexeunclassified

Molekulare Cu^II‐O‐Cu^II‐Komplexe: Stille Wasser sind tief

Haack

Limberg

2014

Angewandte Chemie

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Die Forschung zur O2‐Aktivierung an ligierten CuI‐Ionen wird durch ihre biologische Relevanz und die Suche nach effizienten Oxidationskatalysatoren getrieben. Ein in diesem Zusammenhang selten beobachteter Reaktionspfad ist die ungewöhnliche Bildung von CuII‐O‐CuII‐Einheiten: Ein einzelner, zwischen zwei CuII‐Ionen gebundener Oxoligand erfährt eine beträchtliche Elektronendichte, die Cu2O‐Komplexe sehr reaktiv und somit nur schwer zugänglich macht. Daher – und auch wegen der scheinbar fehlenden biologischen Bedeutung – wurden bisher nur wenige solche Verbindungen synthetisiert und charakterisiert. Kürzlich jedoch wurden CuII‐O‐CuII‐Einheiten als aktive Spezies für die selektive Oxidation von Methan zu Methanol sowohl auf der Oberfläche eines kupferhaltigen Zeoliths als auch im aktiven Zentrum der Methanmomooxygenase diskutiert. Dieser Kurzaufsatz soll einen Überblick über den aktuellen Wissensstand bezüglich niedermolekularer Systeme bieten, mit einem Fokus auf ihren spektroskopischen Eigenschaften und Reaktivitäten.

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“…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%

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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Homogeneous oxidative coupling catalysts. Properties of the oxidative coupling initiator obtained from the reaction of copper(I) chloride with oxygen in pyridine

Cited by 36 publications

References 4 publications

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Molekulare Cu^II‐O‐Cu^II‐Komplexe: Stille Wasser sind tief

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

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Homogeneous oxidative coupling catalysts. Properties of the oxidative coupling initiator obtained from the reaction of copper(I) chloride with oxygen in pyridine

Cited by 36 publications

References 4 publications

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4,5,6-tetrachlorocatecholato Ligand

Molekulare CuII‐O‐CuII‐Komplexe: Stille Wasser sind tief

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

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Molekulare Cu^II‐O‐Cu^II‐Komplexe: Stille Wasser sind tief