Contrast in the effect of penta-amminecobalt(III) on the chemical properties of nicotineamide and isonicotineamide ligands

Haim Cohem; Dan Meyerstein

doi:10.1039/DT9760001976

Contrast in the effect of penta-amminecobalt(III) on the chemical properties of nicotineamide and isonicotineamide ligands

Haim Cohem, Dan Meyerstein

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Abstract

The specific rates of reaction of hydroxyl radicals with L, HL⁺, and [CO(NH₃)₅L]³⁺ [L = pyridine (py), nicotineamide (na), and isonicotineamide (ina)] have been measured. The order k(OH + L) > k{OH + [Co(NH₃)₅L]³⁺} > k(OH + HL+) occurs with the exception k{OH + [Co(NH₃)₅(na)]³⁺} > k(OH + na). The spectra of the intermediates L·OH and [Co^III(NH₃)₅(L·OH)] formed in these reactions have been measured. The spectra of L·OH are similarto those of [Co^III(NH₃)₅(L·OH)] for L = py and ina. However, λ_max = 385 nm for the intermediate formed in the reaction OH + [Co(NH₃)₅(na)]³⁺ whereas λ_max = 315 nm for na·OH. Furthermore the radical [(NCS)]₂^- reacts with [Co(NH₃)₅(na)]³⁺ with k = 3.3 × 10⁸ dm³ mol^-1 s^-1 although it does not react with na and with py, ina, and their complexes. These results are discussed.

Original language	English
Pages (from-to)	1976-1979
Number of pages	4
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	19
DOIs	https://doi.org/10.1039/DT9760001976
State	Published - 1 Dec 1976
Externally published	Yes

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General Chemistry

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title = "Contrast in the effect of penta-amminecobalt(III) on the chemical properties of nicotineamide and isonicotineamide ligands",

abstract = "The specific rates of reaction of hydroxyl radicals with L, HL+, and [CO(NH3)5L]3+ [L = pyridine (py), nicotineamide (na), and isonicotineamide (ina)] have been measured. The order k(OH + L) > k{OH + [Co(NH3)5L]3+} > k(OH + HL+) occurs with the exception k{OH + [Co(NH3)5(na)]3+} > k(OH + na). The spectra of the intermediates L·OH and [CoIII(NH3)5(L·OH)] formed in these reactions have been measured. The spectra of L·OH are similarto those of [CoIII(NH3)5(L·OH)] for L = py and ina. However, λmax = 385 nm for the intermediate formed in the reaction OH + [Co(NH3)5(na)]3+ whereas λmax = 315 nm for na·OH. Furthermore the radical [(NCS)]2- reacts with [Co(NH3)5(na)]3+ with k = 3.3 × 108 dm3 mol-1 s-1 although it does not react with na and with py, ina, and their complexes. These results are discussed.",

author = "Haim Cohem and Dan Meyerstein",

year = "1976",

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doi = "10.1039/DT9760001976",

language = "English",

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journal = "Journal of the Chemical Society. Dalton Transactions",

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T1 - Contrast in the effect of penta-amminecobalt(III) on the chemical properties of nicotineamide and isonicotineamide ligands

AU - Cohem, Haim

AU - Meyerstein, Dan

PY - 1976/12/1

Y1 - 1976/12/1

N2 - The specific rates of reaction of hydroxyl radicals with L, HL+, and [CO(NH3)5L]3+ [L = pyridine (py), nicotineamide (na), and isonicotineamide (ina)] have been measured. The order k(OH + L) > k{OH + [Co(NH3)5L]3+} > k(OH + HL+) occurs with the exception k{OH + [Co(NH3)5(na)]3+} > k(OH + na). The spectra of the intermediates L·OH and [CoIII(NH3)5(L·OH)] formed in these reactions have been measured. The spectra of L·OH are similarto those of [CoIII(NH3)5(L·OH)] for L = py and ina. However, λmax = 385 nm for the intermediate formed in the reaction OH + [Co(NH3)5(na)]3+ whereas λmax = 315 nm for na·OH. Furthermore the radical [(NCS)]2- reacts with [Co(NH3)5(na)]3+ with k = 3.3 × 108 dm3 mol-1 s-1 although it does not react with na and with py, ina, and their complexes. These results are discussed.

AB - The specific rates of reaction of hydroxyl radicals with L, HL+, and [CO(NH3)5L]3+ [L = pyridine (py), nicotineamide (na), and isonicotineamide (ina)] have been measured. The order k(OH + L) > k{OH + [Co(NH3)5L]3+} > k(OH + HL+) occurs with the exception k{OH + [Co(NH3)5(na)]3+} > k(OH + na). The spectra of the intermediates L·OH and [CoIII(NH3)5(L·OH)] formed in these reactions have been measured. The spectra of L·OH are similarto those of [CoIII(NH3)5(L·OH)] for L = py and ina. However, λmax = 385 nm for the intermediate formed in the reaction OH + [Co(NH3)5(na)]3+ whereas λmax = 315 nm for na·OH. Furthermore the radical [(NCS)]2- reacts with [Co(NH3)5(na)]3+ with k = 3.3 × 108 dm3 mol-1 s-1 although it does not react with na and with py, ina, and their complexes. These results are discussed.

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DO - 10.1039/DT9760001976

M3 - Article

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SN - 1472-7773

SP - 1976

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JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

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Contrast in the effect of penta-amminecobalt(III) on the chemical properties of nicotineamide and isonicotineamide ligands

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