Kinetics and mechanism of acid and base hydrolysis of cis-chloro and bromo-(cyclohexylamine)bis-(ethylenediamine) cobalt(III) complexes

Mullick, Nivedita; Nanda, Rabindra K.

doi:10.1016/0022-1902(72)80018-6

Journal of Inorganic and Nuclear Chemistry

1972

DOI: 10.1016/0022-1902(72)80018-6

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Kinetics and mechanism of acid and base hydrolysis of cis-chloro and bromo-(cyclohexylamine)bis-(ethylenediamine) cobalt(III) complexes

Nivedita Mullick¹,

Rabindra K. Nanda²

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Cited by 5 publications

References 15 publications

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The kinetics of aquation and racemization of some cis‐ chloro‐, hydroxo‐, and aquabis(ethylenediamine)(amine)cobalt(III) complexes

Fenemor

House

1976

Int J of Chemical Kinetics

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Aquation rates forcis‐CoCl(en)2(A)2+ (A = 3,5‐lutidine, imidazole, N‐methylimidazole, benzimidazole) have been determined by halide release titration in 1.0 M HNO3 at 50–80°C. Kinetic parameters are (in the above order of A) 107k298 (sec−1), 7.4, 5.7, 1.3, 9.7; Ea (kJ/mole), 103, 101, 130, 112; log PZ (sec−1), 11.89, 11.53, 16.04, 13.58; ΔS298‡ (J/°K· mole),−26, −32, +54,+7. Rates of racemization for active cis‐Co(en)2(A)‐(OH2)3+ were measured spectropolarimetrically in 0.1 M HClO4, 0.02 M Hg2+ for A = ammonia, cyclohexylamine, 3,5‐lutidine, N‐methylimidazole. Kinetic parameters are (units as above) 109k298 = 1.8, 38.0, 7.7, 1.7; Ea = 150, 135, 152, 157; log PZ = 17.49, 16.18, 18.56, 18.87; ΔS298‡ = +82, +57, +102,+108. Rates of racemization of the active hydroxo complexes cis‐Co(en)2(A)(OH)2+ (A = NH3, CH3NH2, 3,5‐lutidine, imidazole) were measured similarly at pH = 8 (π = 2.0, NaClO4). The racemization of the hydroxo is ca. (3–4) × 103 faster than for the corresponding aqua complex. Kinetic parameters are 106k298 = 2.55, 7.2, 30.1, 7.0; Ea = 138, 123, 122, 128; log PZ = 18.58, 16.39, 16.85, 17.18; ΔS298‡ = +102,+60, +69,+76. Racemization rates for aquahydroxo mixtures (A = CH3NH2, 3,5‐lutidine, imidazole) were also determined in the pH range of 4–8 (θ = 2.0, NaClO4) at 50.6°C, and pKa data calculated from the pH versus k plot are 5.50, 5.65, and 6.40, respectively, for A.

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The kinetics of aquation and racemization of some cis‐ chloro‐, hydroxo‐, and aquabis(ethylenediamine)(amine)cobalt(III) complexes

Fenemor

House

1976

Int J of Chemical Kinetics

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Kinetics and mechanism of acid and base hydrolysis ofcis-chloro-(benzotriazole)bis(ethylenediamine)cobalt(III) andcis-chloro-(N-methylbenzotriazole)bis(ethylenediamine)cobalt(III) cations

Rao

Nanda

Tripathy

1981

Transition Met Chem

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Stereochemistry and reaction rates of anionopentaamine complexes of cobalt(III) and chromium(III)

House

1977

Coordination Chemistry Reviews

100

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Kinetics and mechanism of acid and base hydrolysis of cis-chloro and bromo-(cyclohexylamine)bis-(ethylenediamine) cobalt(III) complexes

Cited by 5 publications

References 15 publications

The kinetics of aquation and racemization of some cis‐ chloro‐, hydroxo‐, and aquabis(ethylenediamine)(amine)cobalt(III) complexes

The kinetics of aquation and racemization of some cis‐ chloro‐, hydroxo‐, and aquabis(ethylenediamine)(amine)cobalt(III) complexes

Kinetics and mechanism of acid and base hydrolysis ofcis-chloro-(benzotriazole)bis(ethylenediamine)cobalt(III) andcis-chloro-(N-methylbenzotriazole)bis(ethylenediamine)cobalt(III) cations

Stereochemistry and reaction rates of anionopentaamine complexes of cobalt(III) and chromium(III)

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