Kupferproteine: Koordination und Aktivierung von Sauerstoff und seine Reduktion zu Wasser

Solomon, Edward I.; Chen, Peng; Metz, Markus; Lee, Sang‐Kyu; Palmer, Amy E.

doi:10.1002/1521-3757(20011217)113:24<4702::aid-ange4702>3.0.co;2-6

Cited by 120 publications

(44 citation statements)

References 79 publications

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“…The reaction of equimolar amounts of CuA C H T U N G T R E N N U N G (OTf) 2 and K[L1] resulted in the isolation of a light blue complex. According to elemental analysis, a complex of stoichiometric amounts of copper(II), ligand and anion is formed, which we label as [1]…”

Section: Synthesis Of Copper(ii) Complexesmentioning

confidence: 99%

“…[1] Currently, up to seven different types of copper sites in proteins can be discerned on the basis of structure and spectroscopy of their active site, and they feature mono-, di-, tri-or tetranuclear copper centres. [2] The type-3 active sites of copper proteins, for instance, consist of two copper(II) ions in close proximity, both of which are coordinated by three histidine residues.…”

Section: Introductionmentioning

confidence: 99%

“…[19] Furthermore, the four sharp bands observed at 1259, 1224, 1148 and 1028 cm À1 are indicative of the presence of uncoordinated triflate anions. [20][21][22] Further insight into the structure of [1] …”

mentioning

confidence: 99%

“…In addition, a signal observed at m/z 518.63 can be attributed to trinuclear copper species [Cu 3 (L1) 3 A C H T U N G T R E N N U N G (OTf)] 2 + (calcd 518.53). The molar conductivity of 243 cm 2 mol À1 W À1 for a 1 mm solution of [1]A C H T U N G T R E N N U N G (OTf) in acetonitrile lies in the reported range for 2:1 electrolytes. [23] In addition, a d-d transition was observed at 636 nm in the electronic spectrum of [1]A C H T U N G T R E N N U N G (OTf) in acetonitrile.…”

mentioning

confidence: 99%

“…These data could not be fitted to a "simple" dinuclear species. Efforts to grow crystals of [1]-A C H T U N G T R E N N U N G (OTf) suitable for X-ray crystallography have failed so far.…”

mentioning

confidence: 99%

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Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid

Bruijnincx

Viciano‐Chumillas

Lutz

et al. 2008

Chemistry A European J

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Copper(II) complexes of the potentially tripodal N,N,O ligand 3,3‐bis(1‐methylimidazol‐2‐yl)propionate (L1) and its conjugate acid HL1 have been synthesised and structurally and spectroscopically characterised. The reaction of equimolar amounts of ligand and CuII resulted in the complexes [Cu(L1)]n(X)n (X=OTf−, PF6−; n=1,2), for which a new bridging coordination mode of L1 is inferred. Although these complexes showed moderate catecholase activity in the oxidation of 3,5‐di‐tert‐butylcatechol, surprising reactivity with the pseudo‐substrate tetrachlorocatechol was observed. A chloranilato‐bridged dinuclear CuII complex was isolated from the reaction of [Cu(L1)]n(PF6)n with tetrachlorocatechol. This stoichiometric oxidative double dehalogenation of tetrachlorocatechol to chloranilic acid by a biomimetic copper(II) complex is unprecedented. The crystal structure of the product, [Cu2(ca)Cl2(HL1)2], shows a bridging bis‐bidentate chloranilato (ca) ligand and ligand L1 coordinated as its conjugate acid (HL1) in a tridentate fashion. Magnetic susceptibility studies revealed weak antiferromagnetic coupling (J=−35 cm−1) between the two copper centres in the dinuclear complex. Dissolution of the green complex [Cu2(ca)Cl2(HL1)2] resulted in the formation of new pink‐purple mononuclear compound [Cu(ca)(HL1)(H2O)], the crystal structure of which was determined. It showed a terminal bidentate chloranilato ligand and N,N‐bidentate coordination of ligand HL1, which illustrates the flexible coordination chemistry of ligand L1.

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Section: Synthesis Of Copper(ii) Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

“…These data could not be fitted to a "simple" dinuclear species. Efforts to grow crystals of [1]-A C H T U N G T R E N N U N G (OTf) suitable for X-ray crystallography have failed so far.…”

mentioning

confidence: 99%

See 3 more Smart Citations

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid

Bruijnincx

Viciano‐Chumillas

Lutz

et al. 2008

Chemistry A European J

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Biokatalytisch relevante rautenförmige Bis(μ-oxo)dimetall-Kerne in Kupfer- und Eisenkomplexen

Que

Tolman

2002

Angew. Chem.

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Obwohl es in der Chemie des hochvalenten Mangans recht häufig anzutreffen ist, wurde das rautenförmige Strukturmotiv des M2(μ‐O)2‐Kerns für M=Cu oder Fe erst vor kurzem in synthetischen Komplexen entdeckt. Die strukturelle und spektroskopische Charakterisierung dieser reaktiven Cu2(μ‐O)2‐ und Fe2(μ‐O)2‐Verbindungen wurde möglich durch die Verwendung von Hilfsliganden mit geeignetem Design, Methoden zur Handhabung bei tiefen Temperaturen und Messverfahren wie der Elektrospray‐Ionisierungs‐Massenspektrometrie und der Röntgenkristallographie mit Flächenzählern für schnelle Datensammlung. Trotz Unterschieden in den Elektronenstrukturen weisen Cu2(μ‐O)2‐ und Fe2(μ‐O)2‐Kerne analoge kovalente Metall‐Oxo‐Bindungen, bemerkenswert deckungsgleiche Signalmuster im Raman‐ und Röntgenabsorptionsspektrum sowie eine ähnliche Neigung zur Abstraktion von Wasserstoffatomen aus Substraten auf. Eine weitere gemeinsame Eigenschaft im Zusammenhang mit der Reaktivität ist die Kernisomerisierung, auch wenn dabei unterschiedliche Reaktionswege beschritten werden; bei Fe wurde eine Wanderung des Oxoliganden von einer verbrückenden in eine terminale Position festgestellt, während bei Cu die reversible Bildung einer O‐O‐Bindung beobachtet wurde, die ein Peroxoisomer ergibt. Unser Verständnis der Biokatalyse wurde durch die Isolierung und umfassende Charakterisierung der Cu2(μ‐O)2‐ und Fe2(μ‐O)2‐Komplexe bedeutend vertieft. Insbesondere haben sich dadurch neue Vorstellungen zum Funktionsmechanismus von Nichthäm‐Multimetallenzymen wie Methan‐Monooxygenase, Fettsäure‐Desaturase oder Tyrosinase bei der Disauerstoffaktivierung ergeben, über die eine Vielfalt von organischen Umwandlungen katalysiert wird.

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Bis(μ-oxo)dimetal “Diamond” Cores in Copper and Iron Complexes Relevant to Biocatalysis

Que

Tolman

2002

Angew. Chem. Int. Ed.

395

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Although quite a familiar feature in high‐valent manganese chemistry, the M2(μ‐O)2 diamond core motif has only recently been found in synthetic complexes for M=Cu or Fe. Structural and spectroscopic characterization of these more reactive Cu2(μ‐O)2 and Fe2(μ‐O)2 compounds has been possible through use of appropriately designed supporting ligands, low‐temperature handling methods, and techniques such as electrospray ionization mass spectrometry and X‐ray crystallography with area detector instrumentation for rapid data collection. Despite differences in electronic structures that have been revealed through experimental and theoretical studies, Cu2(μ‐O)2 and Fe2(μ‐O)2 cores exhibit analogously covalent metal–oxo bonding, remarkably congruent Raman and extended X‐ray absorption fine structure (EXAFS) signatures, and similar tendencies to abstract hydrogen atoms from substrates. Core isomerization is another common reaction attribute, although different pathways are traversed; for Fe, bridge‐to‐terminal oxo migration has been discovered, while for Cu, reversible formation of an O−O bond to yield a peroxo isomer has been identified. Our understanding of biocatalysis has been enhanced significantly through the isolation and comprehensive characterization of the Cu2(μ‐O)2 and Fe2(μ‐O)2 complexes. In particular, it has led to the development of new mechanistic notions about how non‐heme multimetal enzymes, such as methane monooxygenases, fatty acid desaturase, and tyrosinase, may function in the activation of dioxygen to catalyze a diverse array of organic transformations.

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Kupferproteine: Koordination und Aktivierung von Sauerstoff und seine Reduktion zu Wasser

Cited by 120 publications

References 79 publications

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid

Biokatalytisch relevante rautenförmige Bis(μ-oxo)dimetall-Kerne in Kupfer- und Eisenkomplexen

Bis(μ-oxo)dimetal “Diamond” Cores in Copper and Iron Complexes Relevant to Biocatalysis

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Kupferproteine: Koordination und Aktivierung von Sauerstoff und seine Reduktion zu Wasser

Cited by 120 publications

References 79 publications

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired CuII Complex: Formation of Chloranilic Acid

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired CuII Complex: Formation of Chloranilic Acid

Biokatalytisch relevante rautenförmige Bis(μ-oxo)dimetall-Kerne in Kupfer- und Eisenkomplexen

Bis(μ-oxo)dimetal “Diamond” Cores in Copper and Iron Complexes Relevant to Biocatalysis

Contact Info

Product

Resources

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Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid

Oxidative Double Dehalogenation of Tetrachlorocatechol by a Bio‐Inspired Cu^II Complex: Formation of Chloranilic Acid