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Reversible dioxygen binding and arene hydroxylation reactions: Kinetic and thermodynamic studies involving ligand electronic and structural variations.

ABSTRACT: Copper-dioxygen interactions are of intrinsic importance in a wide range of biological and industrial processes. Here, we present detailed kinetic/thermodynamic studies on the O(2)-binding and arene hydroxylation reactions of a series of xylyl-bridged binuclear copper(I) complexes, where the effects of ligand electronic and structural elements on these reactions are investigated. Ligand 4-pyridyl substituents influence the reversible formation of side-on bound ?-?(2):?(2)-peroxodicopper(II) complexes, with stronger donors leading to more rapid formation and greater thermodynamic stability of product complexes [Cu(II) (2)((R)XYL)(O(2) (2-))](2+). An interaction of the latter with the xylyl ?-system is indicated. Subsequent peroxo electrophilic attack on the arene leads to C-H activation and oxygenation with hydroxylated products [Cu(II) (2)((R)XYLO(2-))((-)OH)](2+) being formed. A related unsymmetrical binucleating ligand was also employed. Its corresponding O(2)-adduct [Cu(II) (2)(UN)(O(2) (2-))](2+) is more stable, but primarily because the subsequent decay by hydroxylation is in a relative sense slower. The study emphasizes how ligand electronic effects can and do influence and tune copper(I)-dioxygen complex formation and subsequent reactivity.

SUBMITTER: Karlin KD

PROVIDER: S-EPMC3570229 | biostudies-literature | 2012 Jul

REPOSITORIES: biostudies-literature

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Reversible dioxygen binding and arene hydroxylation reactions: Kinetic and thermodynamic studies involving ligand electronic and structural variations.

Karlin Kenneth D KD Zhang Christiana Xin CX Rheingold Arnold L AL Galliker Benedikt B Kaderli Susan S Zuberbühler Andreas D AD

Inorganica chimica acta 20120202

Copper-dioxygen interactions are of intrinsic importance in a wide range of biological and industrial processes. Here, we present detailed kinetic/thermodynamic studies on the O(2)-binding and arene hydroxylation reactions of a series of xylyl-bridged binuclear copper(I) complexes, where the effects of ligand electronic and structural elements on these reactions are investigated. Ligand 4-pyridyl substituents influence the reversible formation of side-on bound μ-η(2):η(2)-peroxodicopper(II) comp ...[more]

PMID: 23420124

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Project description:The reactivity between a thiolate-ligated five-coordinate complex [FeII(SMe2N4(tren))]+ (1) and dioxygen is examined in order to determine if O2 activation, resembling that of the metalloenzyme cytochrome P450, can be promoted even when O2 binds cis, as opposed to trans, to a thiolate. Previous work in our group showed that [FeII(SMe2N4(tren))]+ (1) reacts readily with superoxide (O2-) in the presence of a proton source to afford H2O2 via an Fe(III)-OOH intermediate, thus providing a biomimetic model for the metalloenzyme superoxide reductase (SOR). Addition of O2 to 1 affords binuclear mu-oxo-bridged [FeIII(SMe2N4(tren))]2(mu2-O)(PF6)2.3MeCN (3). At low temperatures, in protic solvents, an intermediate is detected, the details of which will be the subject of a separate paper. Although the thiolate ligand does not appear to perturb the metrical parameters of the unsupported mu-oxo bridge (Fe-O= 1.807(8) A, and Fe-O-Fe= 155.3(5) degrees fall in the usual range), it decreases the magnetic coupling between the irons (J=-28 cm(-1)) and creates a rather basic oxo site. Protonation of this oxo using strong (HBF4, HCl) or weak (HOAc, NH4PF6, LutNHCl) acids results in bridge cleavage to cleanly afford the corresponding monomeric anion-ligated (OAc- (6), or Cl- (7)) or solvent-ligated (MeCN (4)) derivatives. Addition of OH- converts [FeIII(SMe2N4(tren))(MeCN2+ (4) back to mu-oxo 3. Thus, mu-oxo bridge cleavage is reversible. The protonated mu-hydroxo-bridged intermediate is not observed. In an attempt to prevent mu-oxo dimer formation, and facilitate the observation of O2-bound intermediates, a bulkier tertiary amine ligand, tren-Et4= N-(2-amino-ethyl)-N-(2-diethylamino-ethyl)-N',N'-diethyl-ethane-1,2-diamine, and the corresponding [FeII(SMe2N4(tren-Et4))]+ (5) complex was synthesized and structurally characterized. Steric repulsive interactions create unusually long FeII-N(3,4) amine bonds in 5 (mean distance=2.219(1) A). The [(tren-Et4)N4SMe2]1- ligand is unable to accommodate iron in the +3 oxidation state, and consequently, in contrast to most thiolate-ligated Fe(II) complexes, [FeII(SMe2N4(tren-Et4))]+ (5) does not readily react with O2. Oxidation of 5 is irreversible, and the potential (Epa=+410 mV (vs SCE)) is anodically shifted relative to 1 (E1/2=-100 mV (vs SCE)).

Dataset Information

Reversible dioxygen binding and arene hydroxylation reactions: Kinetic and thermodynamic studies involving ligand electronic and structural variations.

Publications

Reversible dioxygen binding and arene hydroxylation reactions: Kinetic and thermodynamic studies involving ligand electronic and structural variations.

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