852675-42-4Relevant academic research and scientific papers
Mechanistic investigation of the oxidative addition reactions between different iridium (I) cyclooctadiene ([Ir(LL′)(cod)]) complexes and iodomethane
Theron, Melanie,Grobbelaar, Ebeth,Purcell, Walter,Basson, Stephen S.
, p. 2457 - 2463 (2008/10/09)
The oxidative addition reactions between two different [Ir(cod)(LL′)] complexes (LL′ = hpt and AnMetha) and iodomethane was kinetically investigated. The rate of oxidative addition was determined as 2.2(2) × 10-2 and 2.69(6) × 10-2 M-1 s -1 for [Ir(cod)(hpt)] and [Ir(cod)(AnMetha)] in nitromethane respectively. The large negative entropy of activation for the above-mentioned reactions in different solvents clearly point to an associative mechanism. An intrinsic volume of activation of -30.5(3) and -28(3) cm3 mol -1 was determined for [Ir(cod)(hpt)] and [Ir(cod)(AnMetha)], respectively. A linear transition state with large charge separation and central ion contraction due to oxidation, contributes to the negative volume of activation.
