Comparative Studies on Prussian Blue or Diaquatetraamine-cobalt(III) Promoted Hydrolysis of 4-Nitrophenylphosphate in Microemulsions

International Journal of Molecular Sciences

关键词: Nitrophenyl phosphate;    Hydrolysis;    Microemulsion;    TetraamineCobalt(III);    Mixed valence bimetallic center;   

DOI  :  10.3390/i4060362

来源: mdpi

【 摘 要 】

Comparative reactivities of three diaqua(tetraamine)Co(III) complexes towards hydrolysis of 4-nitrophenyl phosphate was undertaken. The results were contrasted with prussian blue promoted hydrolysis of 4-nitrophenyl phosphate. The tetraamineCobalt(III) complexes accelerated the hydrolytic reaction to varying degrees with the following reactivity order. [(tn)₂Co(OH₂)₂]³⁺ < [(trpn)Co(OH₂)₂]³⁺ < [(tme)₂Co(OH₂)₂]³⁺ [ tn = trimethylenediamine; tme = 1,1,2,2-tetramethyl-1,2-diaminoethane; trpn = tris(3-aminopropyl)amine].These observations are attributed to the active aquo-hydroxo forms of the tetraamineCobalt(III) complexes. The hydrolysis rate for prussian blue promoted hydrolysis was comparable to that obtained for [(tme)₂Co(OH₂)₂]³⁺. The mixed valence bimetallic centers of prussian blue aid in substrate binding and organizing the nitrophenyl phosphate for effective intramolecular nucleophilic attack by coordinated hydroxide or water.

【 授权许可】

Unknown   
2003 by MDPI (http://www.mdpi.org).