Isomerization, solvolysis, ion association, and solvation of cis- and trans-dichlorobis(ethylenediamine)cobalt(III) cations in protic and in dipolar aprotic solvents

Fitzgerald, WR; Parker, A. J.; Watts, D. W.

doi:10.1021/ja01023a015

Cited by 20 publications

(4 citation statements)

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“…The observation that NH 4 Cl is significantly better than NaCl in stabilizing the β-cis isomer could be attributed to the higher ability of this salt to hydrogen bond to the β-cis isomer of the vanadium(V) anion. It is possible that one isomer must form slightly stronger interactions than the other; a VO 2 unit and one carboxylate group in the α-cis isomer may be slightly better hydrogen bond acceptors than two carboxylate groups and one oxovanadium group in the β-cis isomer .…”

Section: Resultsmentioning

confidence: 99%

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹

et al. 1996

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The solution properties of two isomeric forms of the V−EDDA complex (the symmetric α-cis and asymmetric β-cis) have been studied using multinuclear NMR spectroscopy. The isomerization constant of the aqueous equilibrium mixture expressed as [α-cis]/[β-cis] increased on the addition of organic solvents (methanol, formamide, and DMSO) and decreased on the addition of salts (NaCl, NaClO4, and NH4Cl). The isomerization constant and corresponding thermodynamic parameters were determined under a variety of conditions. The solution studies were consistent with the interpretation that solvation is the major contributor to isomer stability. Solid state characterization of the β-cis isomer of NH4[VO2(EDDA)] confirmed this conclusion and allowed detailed examination of the role of hydrogen bonding in this complex. The structural parameters for this complex are triclinic, P1̄, a = 6.787(1) Å, b = 7.272(1) Å, c = 11.014(1) Å, α = 95.084(9)°, β = 92.805(8)°, and γ = 100.009(9)°. The dynamic processes of these complexes were examined in water and in water−DMSO mixtures resulting in observation of an unknown intramolecular dynamic process. The extent to which this complex responds to the environment is discussed, and its implications for biological studies and the mechanism of action of vanadium compounds are briefly considered.

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Section: Resultsmentioning

confidence: 99%

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹

et al. 1996

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“…In any event, it appears that our present findings do not detract from the usefulness of the extensive contributions of Watts' school (13,(33)(34)(35)(36)(37) and others (e.g., 11) in this field, but future work should include routine checks for con.jugate base and redox pathways.…”

Section: Resultsmentioning

confidence: 56%

Kinetics and mechanism of substitution reactions of (dimethylsulfoxide)pentaamminecobalt(III) ion in dimethylsulfoxide solvent: complications due to redox and conjugate base processes

Lo¹,

Oudeman²,

Hansen³

et al. 1976

Can. J. Chem.

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. Can. J. Chem. 54, 3685 (1976).Siniple anation and solvent exchange reactions of Co(NH3)jDMSO3+ in DMSO are acconipanied by reactions in which the conjugate base of this coniplex undergoes either internal redox to cobalt(11) or relatively rapid substitution. These conjugate base reactions are eliminated by addition of H+, although a minor redox pathuay persists Llithin ion pairs of C O ( N H~)~D M S O~+ with chloride or bromide. The latter pathway is evidently not niechanistically related to the solvent exchange or anation reactions. which proceed by dissociative interchange (Id) according to the acti\ation parameters (\olun~e of activation = +10 cm3 mol-1 for DMSO exchange; enthalpy of activation = 123. 121, and --I26 kJ mol-1 for DMSO exchange and bromide and chloride anation respectively). Enthaipies of activation for solkent exchange and for the Iiniiting anation rate are shown to be better criteria of rnechanianl than the corresponding rate coeficients. S. T. DANNY LO, EVELYN IntroductionWe recently summarized (1) the evidence which indicates that, when water is the solvent, simple substitution reactions of cobalt(lI1) ammines

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“…Regardless of the sophistry it is important to know the effect of solvent and counterion on the stability of isomers, and these aspects have been reviewed adequately in recent years (213). Regardless of the sophistry it is important to know the effect of solvent and counterion on the stability of isomers, and these aspects have been reviewed adequately in recent years (213).…”

Section: Certainly Effects Of This Nature Account For Large Changes mentioning

confidence: 99%

Rearrangement in Coordination Complexes

Jackson¹,

Sargeson²

1980

Organic Chemistry: A Series of Monographs

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Isomerization, solvolysis, ion association, and solvation of cis- and trans-dichlorobis(ethylenediamine)cobalt(III) cations in protic and in dipolar aprotic solvents

Cited by 20 publications

References 3 publications

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹

Kinetics and mechanism of substitution reactions of (dimethylsulfoxide)pentaamminecobalt(III) ion in dimethylsulfoxide solvent: complications due to redox and conjugate base processes

Rearrangement in Coordination Complexes

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Isomerization, solvolysis, ion association, and solvation of cis- and trans-dichlorobis(ethylenediamine)cobalt(III) cations in protic and in dipolar aprotic solvents

Cited by 20 publications

References 3 publications

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH4[VO2(EDDA)]1

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH4[VO2(EDDA)]1

Kinetics and mechanism of substitution reactions of (dimethylsulfoxide)pentaamminecobalt(III) ion in dimethylsulfoxide solvent: complications due to redox and conjugate base processes

Rearrangement in Coordination Complexes

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Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹

Factors Affecting Solution Properties of Vanadium(V) Compounds: X-ray Structure of β-cis-NH₄[VO₂(EDDA)]¹