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|Title:||Kinetics of chain reactions between organochromium macrocyclic complexes and iodine||Authors:||Shi, S.
|Issue Date:||27-Dec-1994||Citation:||Shi, S.,Zeng, H.C. (1994-12-27). Kinetics of chain reactions between organochromium macrocyclic complexes and iodine. Journal of Organometallic Chemistry 484 (1-2) : 59-65. ScholarBank@NUS Repository.||Abstract:||The organochromium complexes RCrL(H2O)2+ (R=2-Pr,2-Bu,C6H5CH2, and 4-MeC6H4CH2; L=aneN4) react with I2. When RCrL(H2O)2+ is in excess, the reaction kinetics are dominated by a chain mechanism characterized by a rate law showing half-order dependence on I2 concentration and one-and-a-half-order dependence on RCrL(H2O)2+ concentration. Rate constants for the chain reactions are (M-1 s-1) (1.75 ± 0.07) × 102 for R=2-Pr, (6.50 ± 0.21) × 10 for R=2-Bu, (4.51 ± 0.17) × 10 for R=C6H5CH2, and (1.14 ± 0.08) × 103 4-MeC6H4CH2. The effect of concurrent electrophilic substitution of RCrL(H2O)2+ by I2 is small and varies with the structure of R. The reactivity trend of the family of RCrL(H2O) 2+) (R includes 1°-alkyl, aralkyl, and 2°-alkyl) was discussed in terms of oxidation of RCrL(H2O)2+ and of steric hindrance around the α-carbon of R. © 1994.||Source Title:||Journal of Organometallic Chemistry||URI:||http://scholarbank.nus.edu.sg/handle/10635/91533||ISSN:||0022328X|
|Appears in Collections:||Staff Publications|
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