Theoretical and Experimental Evidence for S_N2 Transition States in Oxidative Addition of Methyl Iodide to cis-[M(CO)₂I₂]^- (M = Rh, Ir)

A molecular mechanics force field for rhodium(I) carbonyl phosphine complexes and its application on the oxidative addition reactions of these complexes

“…These results were also observed during ab initio calculations. 24 The second reaction path during oxidative addition of CH 3 I to Rh(I) Carbonyl Phosphine complexes is an isomerization step (Fig. 1).…”

Prediction of chemical and electrochemical oxidation potentials of β-diketonatobis(triphenylphosphite)rhodium(I) complexes: A DFT study

“…The bent and front TS structures correspond to a side-on approach of the C CH3 -I bond to the rhodium atom. The bent transition state and the linear transition state structure lead to the same intermediate product -a cationic five-coordinated rhodium complex and a free iodide ion [35]. Both the mechanisms of the linear and the bent transition state structures are therefore described as S N 2 processes.…”

“…Three types of transition state (TS) structures have been reported for the oxidative addition of methyl iodide to square planar rhodium(I) complexes [20,34,35]. One type results in cis addition (''front'') and two result in trans addition (''linear'' and ''bent'').…”

Carbon Monoxide as a Chemical Feedstock: Carbonylation Catalysis

“…It is generally accepted that it follows a two-step S N 2 mechanism; nucleophilic attack by the metal on the methyl carbon to displace iodide, presumably with inversion of configuration at the carbon atom, and subsequent iodide coordination to the five-coordinate rhodium complex to give the methyl complex 44 [95,96]. The product of this reaction has been fully characterized spectroscopically [88 a, 97-99].…”