Copper-dioxygen complexes: Functional models for proteins

Kenneth D. Karlin; Dong Heon Lee; Honorio V. Obias; Kristi J. Humphreys

doi:10.1351/pac199870040855

Copper-dioxygen complexes: Functional models for proteins

Kenneth D. Karlin^*
, Dong Heon Lee
, Honorio V. Obias
, Kristi J. Humphreys

^*Corresponding author for this work

Department of Chemistry

Johns Hopkins University

Research output: Contribution to journal › Journal article › peer-review

28 Scopus citations

Abstract

The complex [(TMPA)Cu^ICRCN)]⁺ (1) (TMPA = tris[(2-pyridyl)methyl]amine) binds O₂ forming [{(TMPA)Cu}₂(O₂)]²⁺ (2), with trans-μ-1, 2 peroxo-coordination. Study of complexes with binucleating ligand analogues provide considerable insights and achievement of room-temperature solution stability. Binucleating ligands with tridentate bis[(2-pyridyl)ethyl]amine chelates give side-on μ-η²:η²-peroxo dicopper(II) complexes, likewise in a monooxygenase model system. (P)Fe-X-Cu(L) (P = porphyrinate or binucleating tethered porphyrin; X = O^2-, OH^-) oxidized resting state models of the heme a₃ and CU_B site of cytochrome c oxidase have been generated and characterized, and reduced (P)Fe^II/Cu^I compounds, for O₂ reactivity studies, have been synthesized. A heme/non-heme diiron complex has been generated as a possible model for NO reductase.

Original language	English
Pages (from-to)	855-862
Number of pages	8
Journal	Pure and Applied Chemistry
Volume	70
Issue number	4
DOIs	https://doi.org/10.1351/pac199870040855
State	Published - 1998.04

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@article{e6a4b0d7c93146a2a0abbb5e7ee82ed1,

title = "Copper-dioxygen complexes: Functional models for proteins",

abstract = "The complex [(TMPA)CuICRCN)]+ (1) (TMPA = tris[(2-pyridyl)methyl]amine) binds O2 forming [\{(TMPA)Cu\}2(O2)]2+ (2), with trans-μ-1, 2 peroxo-coordination. Study of complexes with binucleating ligand analogues provide considerable insights and achievement of room-temperature solution stability. Binucleating ligands with tridentate bis[(2-pyridyl)ethyl]amine chelates give side-on μ-η2:η2-peroxo dicopper(II) complexes, likewise in a monooxygenase model system. (P)Fe-X-Cu(L) (P = porphyrinate or binucleating tethered porphyrin; X = O2-, OH-) oxidized resting state models of the heme a3 and CUB site of cytochrome c oxidase have been generated and characterized, and reduced (P)FeII/CuI compounds, for O2 reactivity studies, have been synthesized. A heme/non-heme diiron complex has been generated as a possible model for NO reductase.",

author = "Karlin, \{Kenneth D.\} and Lee, \{Dong Heon\} and Obias, \{Honorio V.\} and Humphreys, \{Kristi J.\}",

year = "1998",

month = apr,

doi = "10.1351/pac199870040855",

language = "English",

volume = "70",

pages = "855--862",

journal = "Pure and Applied Chemistry",

issn = "0033-4545",

number = "4",

}

TY - JOUR

T1 - Copper-dioxygen complexes

T2 - Functional models for proteins

AU - Karlin, Kenneth D.

AU - Lee, Dong Heon

AU - Obias, Honorio V.

AU - Humphreys, Kristi J.

PY - 1998/4

Y1 - 1998/4

N2 - The complex [(TMPA)CuICRCN)]+ (1) (TMPA = tris[(2-pyridyl)methyl]amine) binds O2 forming [{(TMPA)Cu}2(O2)]2+ (2), with trans-μ-1, 2 peroxo-coordination. Study of complexes with binucleating ligand analogues provide considerable insights and achievement of room-temperature solution stability. Binucleating ligands with tridentate bis[(2-pyridyl)ethyl]amine chelates give side-on μ-η2:η2-peroxo dicopper(II) complexes, likewise in a monooxygenase model system. (P)Fe-X-Cu(L) (P = porphyrinate or binucleating tethered porphyrin; X = O2-, OH-) oxidized resting state models of the heme a3 and CUB site of cytochrome c oxidase have been generated and characterized, and reduced (P)FeII/CuI compounds, for O2 reactivity studies, have been synthesized. A heme/non-heme diiron complex has been generated as a possible model for NO reductase.

AB - The complex [(TMPA)CuICRCN)]+ (1) (TMPA = tris[(2-pyridyl)methyl]amine) binds O2 forming [{(TMPA)Cu}2(O2)]2+ (2), with trans-μ-1, 2 peroxo-coordination. Study of complexes with binucleating ligand analogues provide considerable insights and achievement of room-temperature solution stability. Binucleating ligands with tridentate bis[(2-pyridyl)ethyl]amine chelates give side-on μ-η2:η2-peroxo dicopper(II) complexes, likewise in a monooxygenase model system. (P)Fe-X-Cu(L) (P = porphyrinate or binucleating tethered porphyrin; X = O2-, OH-) oxidized resting state models of the heme a3 and CUB site of cytochrome c oxidase have been generated and characterized, and reduced (P)FeII/CuI compounds, for O2 reactivity studies, have been synthesized. A heme/non-heme diiron complex has been generated as a possible model for NO reductase.

UR - https://www.scopus.com/pages/publications/0001476130

U2 - 10.1351/pac199870040855

DO - 10.1351/pac199870040855

M3 - Journal article

AN - SCOPUS:0001476130

SN - 0033-4545

VL - 70

SP - 855

EP - 862

JO - Pure and Applied Chemistry

JF - Pure and Applied Chemistry

IS - 4

ER -

Copper-dioxygen complexes: Functional models for proteins

Abstract

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