Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity.

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Research Abstract Details 

Research Abstract Table of Contents

Jump to the:

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Abstract Text:

Eduardo E ,Biplab Mondal,Thirumanavelan Gandhi,Eunsuk Kim,Nick D Rubie,Pierre ,Kenneth D Karlin,

Heme-Cu/O2 adducts are of interest in the elucidation of the fundamental metal-O2 chemistry occurring in heme-Cu enzymes which effect reductive O-O cleavage of dioxygen to water. In this report, the chemistry of four heme-peroxo-copper [FeIII-(O22-)-CuII]+ complexes (1-4), varying in their ligand architecture, copper-ligand denticity, or both and thus their structures and physical properties are compared in their reactivity toward CO, PPh3, acids, cobaltocene, and phenols. In 1 and 2, the copper(II) ligand is N4-tetradentate, and the peroxo unit is bound side-on to iron(III) and end-on to the copper(II). In contrast, 3 and 4 contain a N3-tridentate copper(II) ligand, and the peroxo unit is bound side-on to both metal ions. CO "displaces" the peroxo ligand from 2-4 to form reduced CO-FeII and CO-CuI species. PPh3 reacts with 3 and 4 displacing the peroxide ligand from copper, forming (porphyrinate)FeIII-superoxide plus CuI-PPh3 species. Complex 2 does not react with PPh3, and surprisingly, 1 reacts neither with PPh3 nor CO, exhibiting remarkable stability toward these reagents. The behavior of 1 and 2 compared to that of 3 and 4 correlates with the different denticity of the copper ligand (tetra vs tridentate). Complexes 1-4 react with HCl releasing H2O2, demonstrating the basic character of the peroxide ligand. Cobaltocene causes the two-electron reduction of 1-4 giving the corresponding micro-oxo [FeIII-(O2-)-CuII]+ complexes, in contrast to the findings for other heme-peroxo-copper species of different design. With t-butyl-substituted phenols, no reaction occurs with 1-4. The results described here emphasize how ligand design and variations influence and control not only the structure and physical properties but also the reactivity patterns for heme-Cu/O2 adducts. Implications for future investigations of protonated heme/Cu-peroxo complexes, low-spin analogues, and ultimately O-O cleavage chemistry are discussed.

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Publishing Authors By Initials

EE ,B Mondal,T Gandhi,E Kim,ND Rubie,P ,KD Karlin,

For similar investigative techniques: chemistry, analytical: scattering, radiation: spectrum analysis, raman research abstracts see: investigative techniques: chemistry, analytical: scattering, radiation: spectrum analysis, raman research

PUBMED ID PMID:

MEDLINE DATE:

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Journal Published:

PUBLICATION TYPE: Research Support, Non-U.S. Gov

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 6382-94

Journal Abbreviation:

ISSN: 0020-1669

DAY: 6

MONTH: 07

YEAR: 2007

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 366543

Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Keywords Mesh Terms:

KEYWORDS: Spectrum Analysis, Raman

MESH TERMS: methods

Chemical & Substance for Abstract: Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity. Information

Substance Name: Oxygen

Registry Number: 7782-44-7

Grant and Affiliation Information for Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity.

AFFILIATION: Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM60353

ACRONYM: GM

MEDLINETA: Inorg Chem

REFSOURCE:

DATABASENAME:

ACCESSION NUMBER:

Number Hits: 0

Reactivity studies on FeIII-O22--CuII compounds: influence of the ligand architecture and copper ligand denticity Related Publications

• A 1:1 copper-dioxygen adduct is an end-on bound superoxo copper(II) complex which undergoes oxygenation reactions with phenols.
• An iron-peroxo porphyrin complex: new synthesis and reactivity toward a Cu(II) complex giving a heme-peroxo-copper adduct.
• Aryl hydroxylation from a mononuclear copper-hydroperoxo species.
• Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes.
• Copper(I) and copper(II) complexes possessing cross-linked imidazole-phenol ligands: structures and dioxygen reactivity.
• Copper(I) complex O(2)-reactivity with a N(3)S thioether ligand: a copper-dioxygen adduct including sulfur ligation, ligand oxygenation, and comparisons with all nitrogen ligand analogues.
• Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry.
• Copper(II)-hydroperoxo complex induced oxidative N-dealkylation chemistry.
• Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation.
• Distinguishing rate-limiting electron versus H-atom transfers in Cu2O2-mediated oxidative N-dealkylations: application of inter- versus intramolecular kinetic isotope effects.
• Exogenous nitrile substrate hydroxylation by a new dicopper-hydroperoxide complex.
• Further insights into the spectroscopic properties, electronic structure, and kinetics of formation of the heme-peroxo-copper complex [(F8TPP)FeIII-(O2(2-)-CuII(TMPA)]+.
• Generation and characterization of [(P)M-(X)-Co(TMPA)]n+ assemblies; P = Porphyrinate, M = FeIII and CoIII, X = O2-, OH-, O2(2-), and TMPA = tris(2-pyridylmethyl)amine.
• Heme/Cu/O2 reactivity: change in FeIII-(O2 2-)-CuII unit peroxo binding geometry effected by tridentate copper chelation.
• Kinetically reduced local Navier-Stokes equations for simulation of incompressible viscous flows.
• Outpatient phototherapy for psoriasis.
• Reaction of elemental sulfur with a copper(I) complex forming a trans-mu-1,2 end-on disulfide complex: new directions in copper-sulfur chemistry.
• Reactivity studies on Fe(III)-(O2(2-))-Cu(II) compounds: influence of the ligand architecture and copper ligand denticity.
• Synthesis and X-ray absorption spectroscopy structural studies of Cu(I) complexes of histidylhistidine peptides: the predominance of linear 2-coordinate geometry.
• Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands.
• Thiol-copper(I) and disulfide-dicopper(I) complex O(2)-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition.
• Tuning copper-dioxygen reactivity and exogenous substrate oxidations via alterations in ligand electronics.
• [Effect of partial pancreatectomy on motor function of the gastrointestinal tract.]
• [Folate content of large mixture of milks. Effect of different thermic treatments on the amount of folates, B12 and B6 of these milks]
• [Formation of the vitamin B12 content in cheeses during preparation, ripening and storage.]
• [ON THE BIOSYNTHESIS OF VITAMIN B12 AND OTHER VITAMINS OF GROUP B BY A CHROMOGENIC BACTERIUM ISOLATED FROM CHEESE.]
• [On the determination of folic acid activity of human blood in controls and in different pathological states]
• [On the enrichment of kefir with vitamin B 12 by addition of Propionibacterium shermanii. Development of levels of different vitamins during preparation and preservation]
• [Studies on variation in the content of vitamin B-6 in human and cow's milk. The effect of pyridoxine on the vitamin content of human milk.]
• [Study on the levels of folic acid in human milk and cow's milk]