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Kinetics and Reaction Mechanisms of Complexes with Cobalt−Carbon σ Bonds of the Type {(NH 3 ) 5 Co−R} n + in Aqueous Solutions, a Pulse Radiolysis Study
Author(s) -
Shaham Nurit,
Masarwa Alexandra,
Matana Yoseph,
Cohen Haim,
Meyerstein Dan
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20021)2002:1<87::aid-ejic87>3.0.co;2-c
Subject(s) - chemistry , radiolysis , aqueous solution , cobalt , kinetics , radical , reaction rate constant , limiting , carbon fibers , photochemistry , inorganic chemistry , organic chemistry , quantum mechanics , engineering , physics , materials science , composite number , composite material , mechanical engineering
The kinetics of formation of complexes with cobalt−carbon σ bonds in the reaction between {Co II (NH 3 ) 5 H 2 O} 2+ or {Co II (NH 3 ) 6 } 2+ with different aliphatic radicals was studied in aqueous solutions using the pulse radiolysis technique. The formation of the complexes {(NH 3 ) 5 Co III −R} n + obey pseudo first order rate laws and the rate constants for R = CH 3 and CH 2 CO 2 − are (3.0±0.3)×10 7 and (2.1±0.3)×10 7 M −1 s −1 , respectively. The UV/Vis spectra of the complexes are reported and found to be in agreement with previous results for analogous complexes. The results point out that the reactions (NH 3 ) 5 Co III −R + R · + NH 3 → Co(NH 3 ) 6 2+ + R 2 are fast thus limiting the radical route as a synthetic tool for the (NH 3 ) 5 Co III −R complexes.