Formation of an observable intermediate during the reduction of [Co-(III)(NH3)(5)CN](2+) by center dot(CRR2)-R-1(OH) radicals

摘要

(CRROH)-C-center dot-R-1-O-2, R-i = CH3 or H, react with the complex [Co-III(NH3)(5) N](2+) to form an observable intermediate probably via bonding to the nitrogen of the cyanide. This intermediate isomerizes to form a second intermediate. The second intermediate decomposes into Co2+(aq), 5NH(4)(+), CN- and (RRCO)-R-1-C-2. The plausible structures of the intermediates are discussed. The radicals (-CH3), (CH2CHO)-C-center dot, (CH)-C-center dot(OH)CO2-, (CH2C)-C-center dot(CH3)(2)OH, CO2center dot- and CH3O2center dot are considerably less reactive towards this complex, the formation of intermediates in their presence is not observed. (c) 2005 Elsevier B.V. All rights reserved.