.mu.-Ligand-.mu.-peroxo-dicobalt(III) cations

Crawford, M. K.; Bedell, Stephen A.; Patel, Rajendra I.; Young, Leroy W.; Nakon, Robert

doi:10.1021/ic50198a004

Cited by 10 publications

(2 citation statements)

References 4 publications

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“…A fit of the spectrum using eight lines is shown in the figure. (24) have demonstrated the formation of pethylenediarnine-k-peroxy complexes by the oxygenation of cobalt amine solutions. We tentatively assign the remaining resonances to complexes of this type.…”

Section: Co(ncs)~'-mentioning

confidence: 99%

A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

Au-Yeung¹,

Eaton²

1983

Can. J. Chem.

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(1983). A simple point charge model has been developed for calculating the chen~ical shifts and linc widths obtained from the "Co nmr spectra of Co(ll1) complcxcs. The chemical shift calculations assume the prcdominance of the paramagnetic term in thc Ramsey equation and thc rclationship of this term to the cnergies of thc d-el electronic transitions. The line width calculations assume the predominance of quadrupolar broadening and use a point charge model to calculate electric field gradients in a manner previously used to interpret Mossbaucr spectra. The model is tested by application to some fifty known Co(l11) complexes. Most of the '"Co spcctra have been remeasured for this purpose. One chemical shift paramctcr and one line width parameter are required for cach different typc of ligand. Thcse paramcters are related to each other and to the crystal field splitting parameters of the ligands. The calculations can be readily applied to complexes of any symmetry and differentiate between different isomers of the same complex. The calculated chemical shifts covcr a range of more than 14 000 ppm and the standard deviation between the calculated and experimental values is 108 ppm. Relative chemical shifts between complexes with similar ligands are calculated with considerably higher accuracy. The agreement between calculated and experimental line widths is only qualitative but the line width calculations provide valuable additional information for making assignments. The model is applied to the assignment of different isomers of cobalt dioxygen compounds and to the identification of products from oxygenation reactions.

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Section: Co(ncs)~'-mentioning

confidence: 99%

A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

Au-Yeung¹,

Eaton²

1983

Can. J. Chem.

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“…Co(en) 3 forms a bridged 2:1 µ-peroxo adduct despite the initial saturation of the metal coordination sites. Previous reported data 56 in aqueous solution on the same system pointed out the formation of a [Co 2 (en) 5 O 2 ] 4+ species with the hypothesized structure reported in Chart 1.…”

Section: Discussionmentioning

confidence: 99%

Cobalt(II) Dioxygen Carriers Based on Simple Diamino Ligands: Kinetic and ab Initio Studies

et al. 2003

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The kinetics of the oxygenation reaction of CoL2(2+) complexes (L=ethylenediamine (en), N,N'-dimethylethylenediamnine (dmen)) have been investigated in dimethyl sulfoxide (dmso) at 298 K and in a medium adjusted to 0.1 mol dm(-3) with Et4NClO4 by means of a UV-vis spectrophotometric technique. The reaction mechanisms are consistent with the fast formation of superoxo 1:1 initial CoL2-O2 species (L=en, dmen), whereas the dimeric mu-peroxo (CoL2)2O2 adduct is formed only when L=en, in the rate determining step. The kinetic results are discussed taking into account the effects of ligand/solvent substitution. EPR results give information on the electronic structure and the coordination geometry of the Co(II) complexes and further confirm the stoichiometry of the species formed. Ab initio calculations provide insights on the geometrical parameters of all the complexes investigated and allow us to draw some hypotheses about the influence of H.H nonbonded interactions in the eventual formation of the dimeric mu-peroxo (CoL2)2O2 complexes. Solvational effects are also considered. The formation of the (CoL3)2O2 adduct is also proved when L=en by means of O2 volumetric absorption.

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ChemInform Abstract: μ‐LIGAND‐μ‐PEROXO‐DICOBALT(III) CATIONS

Crawford¹,

Bedell²,

Patel³

et al. 1979

Chemischer Informationsdienst

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.mu.-Ligand-.mu.-peroxo-dicobalt(III) cations

Cited by 10 publications

References 4 publications

A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

Cobalt(II) Dioxygen Carriers Based on Simple Diamino Ligands: Kinetic and ab Initio Studies

ChemInform Abstract: μ‐LIGAND‐μ‐PEROXO‐DICOBALT(III) CATIONS

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.mu.-Ligand-.mu.-peroxo-dicobalt(III) cations

Cited by 10 publications

References 4 publications

A model for estimating 59Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

A model for estimating 59Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

Cobalt(II) Dioxygen Carriers Based on Simple Diamino Ligands: Kinetic and ab Initio Studies

ChemInform Abstract: μ‐LIGAND‐μ‐PEROXO‐DICOBALT(III) CATIONS

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A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes

A model for estimating ⁵⁹Co nmr chemical shifts and line widths and its application to cobalt dioxygen complexes