Kinetics and mechanism of aquation and formation reactions of carbonato complexes. 14. Base-catalyzed carbonato ring opening of carbonato (.beta.,.beta.',.beta."-triaminotriethylamine) cobalt(III) perchlorate and spontaneous decarboxylation of aquobicarbonato (.beta.,B',B"-triaminotriethylamine) cobalt(III)

Dasgupta, Tara P.; Harris, G. M.

doi:10.1021/ic50189a032

Cited by 11 publications

(3 citation statements)

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“…10,27 On the other hand, the dissociations of cobalt and mixed carbonate-cobalt complexes occur within the stopped-flow time range (subsecond) up to several seconds. 31,38,39 Therefore, CoNtaCO 3 2 − dissociation is not likely to interfere with the very fast process of carbonate and cobalt transfer from CoNtaCO 3 2 − to the C-lobe (Fig. 4, Table 1; Eq.…”

Section: Discussionmentioning

confidence: 99%

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Chikh

Hémadi

Miquel

et al. 2008

Journal of Molecular Biology

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Section: Discussionmentioning

confidence: 99%

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Chikh

Hémadi

Miquel

et al. 2008

Journal of Molecular Biology

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“…[Co(tren)CO3]C10 4 was prepared following the published procedure (Dasgupta & Harris, 1978). A saturated solution of sodium chloride was added to a solution of [Co(tren)COa]C10 4 with stirring.…”

Section: Methodsmentioning

confidence: 99%

“…In recent years, many interesting studies on cobalt(III) and chromium(III) complexes containing tris(2-aminoethyl)amine (fl, fl',ff'-triaminotriethylamine, tren) as a tetradentate ligand have been undertaken (e.g. Dasgupta & Harris, 1971, 1978Madan, Refff &-B~lar, 1965;Zipp & Madan, 1976) since the tripodal nature of the ligand offers a 0108-2701/83/081012-04501.50 stereochemically rigid system. It was observed that the acid-catalyzed Co--O bond breaking rate in [Co(tren)CO3] + is larger than that for the corresponding ethylenediamine and tetraammine analogues (Dasgupta & Harris, 1971).…”

mentioning

confidence: 99%

Carbonato[tris(2-aminoethyl)amine]cobalt(III) chloride trihydrate, [Co(C6H18N4)(CO3)]Cl.3H2O

Schlemper¹,

Gupta²,

Dasgupta³

1983

Acta Crystallogr C

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Abstract. M r=354.7, monoclinic, P21/c, a= 7.177 (1), b= 19.286 (2), c= 10.743 (3)A, fl= 93.86 (4) °, V= 1483.6 (8) A 3, On= 1.58 (1), Ox= 1.588(1)gcm -3, Z=4, 2(MoKt~)=0.7107A, p= 13.6 cm -1, T= 295 (1) K, F(000) = 744. The final discrepancy factors were R F = 2.0% and wR r = 2.7% for those 1985 reflections IF o > 2a(Fo)] in the range 3.5 ° < 20 < 47 °. The Co In ion is surrounded by four N atoms from the tetradentate amine ligand and by two O atoms from the chelated carbonate ligand in a somewhat distorted octahedron, e.g. the angle OCo-O = 68.46 (5) °. One of the Co-O bonds is longer than the other, 1.931(1) and 1.910(1)A, which suggests that the bond breaking during decarboxylation preferentially takes place at the site of the longer bond.

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Ligand‐Substitution Reaction of Cobalt(III) Complexes of [CoCl(N)₅]²⁺‐type with Carbonate: Activation of Kinetic Processes by Steric Chelate Effect

Masuda

Jitsukawa

Masuda

et al. 1995

Ber Bunsenges Phys Chem

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Kinetics and mechanisms of coordination by ligand‐substitution of HCO3− for Cl− on the cobalt(III) complexes of [CoCl(N)5]2+‐type having different (N)5 backbone chelate ring structures to form those of [Co(CO3)(N)5]+‐type have been investigated in a weakly alkaline aqueous 0.10 mol dm−3 sodium perchlorate solution at ambient temperatures, in order to elucidate any possibility for the fixation of atmospheric CO2 on the coordination sphere of the transition metal center in the form of CO2−3. The HCO3− in the aqueous solution easily and substitutionally coordinates to the cobalt(III) complexes in place of coordinated chloro ligand via two consecutive rate‐determining steps, the faster one with two parallel pathways of aquation and hydroxide‐anation and the slower one with a pathway of carbonate‐anation. Of these reaction pathways, the hydroxide‐anation was explained by a dissociative interchange mechanism via conjugate base (IdCB), whereas the carbonate‐anation was explained by a nucleophilic attack of coordinated oxygen atom on the central cobalt(III) atom to the carbon atom of HCO3− while maintaining the Co – O bond throughout the step by taking the result of an EHMO calculation into consideration. The (N)5 backbone chelate ring structure served to enhance the rate of coordination of HCO3− on the cobalt(III) center as well as that of preceding aquation and hydroxide‐anation steps chiefly by its entropy effect. The pentadentate tetren backbone structure was recommended for the rapid fixation of CO2 in the form of CO2−3 on the cobalt(III) complexes of [CoCl(N)5]2+‐type.

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Cited by 11 publications

References 40 publications

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Carbonato[tris(2-aminoethyl)amine]cobalt(III) chloride trihydrate, [Co(C6H18N4)(CO3)]Cl.3H2O

Ligand‐Substitution Reaction of Cobalt(III) Complexes of [CoCl(N)₅]²⁺‐type with Carbonate: Activation of Kinetic Processes by Steric Chelate Effect

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Cited by 11 publications

References 40 publications

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Cobalt and the Iron Acquisition Pathway: Competition towards Interaction with Receptor 1

Carbonato[tris(2-aminoethyl)amine]cobalt(III) chloride trihydrate, [Co(C6H18N4)(CO3)]Cl.3H2O

Ligand‐Substitution Reaction of Cobalt(III) Complexes of [CoCl(N)5]2+‐type with Carbonate: Activation of Kinetic Processes by Steric Chelate Effect

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Ligand‐Substitution Reaction of Cobalt(III) Complexes of [CoCl(N)₅]²⁺‐type with Carbonate: Activation of Kinetic Processes by Steric Chelate Effect