Issue 0, 1970

Reactions of µ-hydroxo-dicobalt complexes. Part II. The kinetics of the µ-amido-µ-hydroxo-bis[tetra-amminecobalt(III)] complex with thiocyanate in aqueous perchloric acid and the characterization of the bisthiocyanate product

Abstract

The thiocyanate, nitrate, and perchlorate salts of the µ-amidobis[thiocyanatotetra-amminecobalt(III)] complex (NH3)4(NCS)Co·NH2·Co(NCS)(NH3)43+ have been prepared and characterized by analyses, ion-exchange, pH, and i.r. techniques. The kinetics of the formation of the complex from the µ-amido-µ-hydroxo-bis[tetra-amminecobalt(III)] complex in perchloric acid solutions, µ= 2·0M(NaClO4), have been studied. A self-consistent interpretation is possible if the µ-amido-[aquotetra-amminecobalt(III)][thiocyanatotetra-amminecobalt(III)] complex which is first formed (k=ca. 2 × 10–3 l. mole–1 sec.–1 at 25°) reacts to give the µ-amido-µ-thiocyanatobis[tetra-amminecobalt(III)] complex in the first stage. It is suggested tentatively that the nitrogen of the thiocyanate is co-ordinated to both cobalt atoms. Protonation (Kp= 0·38 ± 0·04 l. mole–1) occurs before reaction with the second thiocyanate. At 25° the second-order rate constant for the reaction of the protonated form with thiocyanate is k= 1·22 ± 0·16 × 10–3 l. mole–1 sec.–1.

Article information

Article type
Paper

J. Chem. Soc. A, 1970, 1064-1068

Reactions of µ-hydroxo-dicobalt complexes. Part II. The kinetics of the µ-amido-µ-hydroxo-bis[tetra-amminecobalt(III)] complex with thiocyanate in aqueous perchloric acid and the characterization of the bisthiocyanate product

S. W. Foong, M. B. Stevenson and A. G. Sykes, J. Chem. Soc. A, 1970, 1064 DOI: 10.1039/J19700001064

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