Kinetics and mechanism of the oxidative addition of iodomethane to β-diketonatobis(triphenylphosphite)rhodium(I) complexes

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

“…The possibility of a three-centered polar transition state, which normally leads to cis addition, cannot be ruled out 7 ( Fig. 2).…”

High-pressure methods as a tool in organometallic syntheses: facilitation of oxidative addition to platinum(II)

“…[5], the simplest nonlinear regression equation, is acceptable only for interpolation of data at best. Taking these results together with those for the Pd analogue of reaction [3] (19) and oxidative addition at ~h ' centres (14), we conclude that a synthetic organometallic chemist may expect pressure accelerations of oxidative addition reactions of some three orders of magnitude if a 2 GPa press is used.…”

“…-18, -19, and -23 c m h o l -' were found for the trifluorobenzoylacetone complex in 1,2-dichloroethane, dichloromethane, acetone, and chloroform, respectively (14). It therefore would seem that pressure acceleration could be used to advantage to force to useful degrees of completion those oxidative addition reactions that are thermodynamically feasible but normally too slow for practical purposes.…”

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

“…[22]. b Kinetic rate constants 25.0(1)°C in acetone form reference [16,52]. c Acid dissociation constant pK a from Refs.…”

“…Oxidative addition of methyl iodide to rhodium(I) b-diketonato complexes also leads to the formation of a stable rhodium(III) alkyl intermediate or reaction product [11][12][13][14][15][16][17][18][19]. A theoretical study of the oxidative addition of iodomethane to [Rh(CH 3 COCHC-OCH 3 )(P(OPh) 3 ) 2 ] [20] indicates that oxidative addition of iodo methane to [Rh(b-diketonato)(P(OPh) 3 ) 2 ] occurs via a two-step mechanism.…”