Oxidative homolysis of organochromium(III) macrocyclic complexes

✍ Scribed by Shu Shi

• Publisher: Springer
• Year: 1994
• Tongue: English
• Weight: 317 KB
• Volume: 19
• Category: Article
• ISSN: 0340-4285
• DOI: 10.1007/bf00139097

✦ Synopsis

Organochromium complexes, [CrRL(H20)] 2 § (L= 1,4,8,12-tetraazacyclopentadecane; R = 1 ~ or 2~ or para-substituted benzyl), are oxidized to [CrRL(H 20)] 3 +, which rapidly decomposes (k 3 > 102 s-1) by homolysis of the Cr--C bond. Rate constants of the oxidation of these complexes by [IrC16] 2-range from 2.20 x 10-1 (R = Me) to 4.60 x l0 s (R = 4-MeC6H4CHz)dm 3 tool 1 s-a A very negative reaction constant (-4.3) is found for the oxidation ofpara-substituted benzlchromium(III) complexes which, in conjunction with the resul.ts of product analysis, indicates a [Crm/R "] type transmon state.