Dioxygen-copper reactivity.  Models for hemocyanin:  Reversible O2 and CO binding to structurally characterized dicopper(I) complexes containing hydrocarbon-linked bis[2-(2-pyridyl)ethyl]amine units

Karlin, Kenneth D.; Haka, Michael S.; Cruse, Richard W.; Meyer, Gerald J.; Farooq, Amjad; Gultneh, Yilma; Hayes, Jon C.; Zubieta, Jon

doi:10.1021/ja00212a031

Cited by 131 publications

(110 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

103

Contrasting

Order By: Relevance

“…On the basis of comparisons with free ligand 3 and other relevant compounds, the observed resonances have been assigned. As is found for similar cases, the predominating tendency is for a downfield shift of 1 H resonances upon coordination to the positively charged metal ion (coordination-induced shifts) [35] [36]. At room temperature (208) the 1 H-NMR spectra of complexes 5 and 6 show broad peaks for the CH 2 H-atoms.…”

Section: Methodsmentioning

confidence: 61%

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Mandal

Mukherjee

2008

Chemistry & Biodiversity

View full text Add to dashboard Cite

Reaction of a Cu(I) complex of a hybrid tridentate ligand, encompassing [2-(pyridin-2-yl)ethyl]amine and dimethyl-substituted ethylalkylamine with dioxygen, generates in acetone at -80 degrees putative bis(mu-oxo)dicopper(III) intermediate. Structural characterization of a PPh(3)-adduct of a mononuclear Cu(I) complex of this new ligand has been achieved. This ligand coordinates in a facial mode utilizing three N-atoms (-CH(2)CH(2)-Py, -CH(2)CH(2)NMe(2), and -NCH(2)Ph). Reactivity of bis(mu-oxo)dicopper(III) intermediate toward exogenous substrates (2,4-di(tert-butyl)phenol and 2,4,6-tri(tert-butyl)phenol) has also been investigated.

show abstract

Section: Methodsmentioning

confidence: 61%

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Mandal

Mukherjee

2008

Chemistry & Biodiversity

View full text Add to dashboard Cite

show abstract

“…The spectrometer was equipped with a variable-temperature Dewar and cuvette assembly as described elsewhere. 65,66 Variable Temperature NMR Studies. Both deuterated and undeuterated solvents were distilled and degassed prior to use.…”

Section: Methodsmentioning

confidence: 99%

Low-Temperature UV−Visible and NMR Spectroscopic Investigations of O₂ Binding to (⁶L)Fe^II, a Ferrous Heme Bearing Covalently Tethered Axial Pyridine Ligands

Ghiladi

Karlin

2002

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

In this report, we describe the reversible dioxygen reactivity of ((6)L)Fe(II) (1) [(6)L = partially fluorinated tetraphenylporphyrin with covalently appended TMPA moiety; TMPA = tris(2-pyridylmethyl)amine] using a combination of low-temperature UV-vis and multinuclear ((1)H and (2)H) NMR spectroscopies. Complex 1, or its pyrrole-deuterated analogue ((6)L-d(8))Fe(II) (1-d(8)), exhibits downfield shifted pyrrole resonances (delta 28-60 ppm) in all solvents utilized [CH(2)Cl(2), (CH(3))(2)C(O), CH(3)CN, THF], indicative of a five-coordinate high-spin ferrous heme, even when there is no exogenous axial solvent ligand present (i.e., in methylene chloride). Furthermore, ((6)L)Fe(II) (1) exhibits non-pyrrolic upfield and downfield shifted peaks in CH(2)Cl(2), (CH(3))(2)C(O), and CH(3)CN solvents, which we ascribed to resonances arising from the intra- or intermolecular binding of a TMPA-pyridyl arm to the ferrous heme. Upon exposure to dioxygen at 193 K in methylene chloride, ((6)L)Fe(II) (1) [UV-vis: lambda(max) = 433 (Soret), 529 (sh), 559 nm] reversibly forms a dioxygen adduct [UV-vis: lambda(max) = 422 (Soret), 542 nm], formulated as the six-coordinate low-spin [delta(pyrrole) 9.3 ppm, 193 K] heme-superoxo complex ((6)L)Fe(III)-(O(2)(-)) (2). The coordination of the tethered pyridyl arm to the heme-superoxo complex as axial base ligand is suggested. In coordinating solvents such as THF, reversible oxygenation (193 K) of ((6)L)Fe(II) (1) [UV-vis: lambda(max) = 424 (Soret), 542 nm] also occurs to give a similar adduct ((6)L)Fe(III)-(O(2)(-)) (2) [UV-vis: lambda(max) = 418 (Soret), 537 nm. (2)H NMR: delta(pyrrole) 8.9 ppm, 193 K]. Here, we are unable to distinguish between a bound solvent ligand or tethered pyridyl arm as axial base ligand. In all solvents, the dioxygen adducts decompose (thermally) to the ferric-hydroxy complex ((6)L)Fe(III)-OH (3) [UV-vis: lambda(max) = 412-414 (Soret), 566-575 nm; approximately delta(pyrrole) 120 ppm at 193 K]. This study on the O(2)-binding chemistry of the heme-only homonuclear ((6)L)Fe(II) (1) system lays the foundation for a more complete understanding of the dioxygen reactivity of heterobinuclear heme-Cu complexes, such as [((6)L)Fe(II)Cu(I)](+), which are models for cytochrome c oxidase.

show abstract

“…This ligand was prepared with reference to the report by Kahrin et al [22]. A mixture of 2-vinylpyridine (9.7 g, 93 mmol), m-xylilenediamine (1.26 g, 9.3 mmol), and acetic acid (2.8 ml) were …”

Section: Preparation Of M-xylylenedi{bis[2-(2-pyridyl)ethyl]} Amino-nmentioning

confidence: 99%

Random and block copolymerizations of norbornene with conjugated 1,3-dienes catalyzed by novel Ni compounds involving N- or O-donated ligands

Suzuki

Matsumura

Satoh

et al. 2004

Reactive and Functional Polymers

View full text Add to dashboard Cite

Dioxygen-copper reactivity. Models for hemocyanin: Reversible O2 and CO binding to structurally characterized dicopper(I) complexes containing hydrocarbon-linked bis[2-(2-pyridyl)ethyl]amine units

Cited by 131 publications

References 1 publication

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Low-Temperature UV−Visible and NMR Spectroscopic Investigations of O₂ Binding to (⁶L)Fe^II, a Ferrous Heme Bearing Covalently Tethered Axial Pyridine Ligands

Random and block copolymerizations of norbornene with conjugated 1,3-dienes catalyzed by novel Ni compounds involving N- or O-donated ligands

Contact Info

Product

Resources

About

Dioxygen-copper reactivity. Models for hemocyanin: Reversible O2 and CO binding to structurally characterized dicopper(I) complexes containing hydrocarbon-linked bis[2-(2-pyridyl)ethyl]amine units

Cited by 131 publications

References 1 publication

Formation of {Cu(μ‐O)2}2+ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Formation of {Cu(μ‐O)2}2+ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Low-Temperature UV−Visible and NMR Spectroscopic Investigations of O2 Binding to (6L)FeII, a Ferrous Heme Bearing Covalently Tethered Axial Pyridine Ligands

Random and block copolymerizations of norbornene with conjugated 1,3-dienes catalyzed by novel Ni compounds involving N- or O-donated ligands

Contact Info

Product

Resources

About

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Formation of {Cu(μ‐O)₂}²⁺ Core Due to Dioxygen Reactivity of a Copper(I) Complex Supported by a New Hybrid Tridentate Ligand: Reaction with Exogenous Substrates

Low-Temperature UV−Visible and NMR Spectroscopic Investigations of O₂ Binding to (⁶L)Fe^II, a Ferrous Heme Bearing Covalently Tethered Axial Pyridine Ligands