Mechanism for the oxidative addition of lodomethane to carbonyl(N-hydroxy-N-nitrosobenzenaminato-O,O′)triarylphosphinerhodium(I) complexes and crystal structure of [Rh(cupf)(CO)(CH3)(1)(PPh3)]

Methyl iodide oxidative addition to [Rh(acac)(CO)(PPh3)]: an experimental and theoretical study of the stereochemistry of the products and the reaction mechanism

“…Furthermore, as mentioned before, all of the crystal structures of [Rh III (L,L¢-BID)(CH 3 )(CO)(PPh 3 )(I)] complexes (where L,L¢-BID is a monocharged bidentate ligand with donor atoms L and L¢) to date have the CO group in the square plane and the iodide in the apical position (trans to the PPh 3 group). 27,34,40- 43 These results are consistent with the proposed stereochemistry of the Rh III -alkyl2 complex in Scheme 1.…”

Di-μ-iodido-bis[acetyl(4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane)(N-nitroso-N-oxidoaniline-κ2O,O′)rhodium(III)]

“…For the synthesis of similar Rh complexes and information on oxidative addition products, see: Basson et al (1984;1986a,b;1987; Roodt & Steyn (2000); Smit et al (1994); Steyn et al (1992); Van Leewen & Roobeeck (1981).…”

“…The coordination sphere around the metal is somewhat distorted from the octahedral geometry and a number of angles deviate significantly from the ideal (see Table 1). This is probably due to the small bite angle of 78.74 19 (Basson et al, 1987). This stems from the nature of phosphites to be excellent π-acceptors, causing stronger back donation from rhodium resulting in a shorter Rh-P bond.…”

Kinetic Evaluation of Ligand Hemilability in Transition Metal Complexes

“…Moreover, significant solvent effects are observed in these reactions, which proceed by means of an SN2 pathway, in contrast to the lack of any correlation with the solvent donor ability in the clockwise route ( k 1 ) of Scheme . A kinetic pattern showing a nonzero intercept was found once in the case of the rhodium(I) complex [Rh(cupf)(CO)(PPh 3 )], containing the bidentate anionic ligand N ‐nitrosophenyloxyamine PhN(NO)O – (cupf) 21. In this case, the presence of mixed first‐ and second‐order pathways was interpreted as the result of an intramolecular rearrangement of the complex induced by the attack of solvent and involving a change of the coordinative mode of the bifunctional ligand, thus generating a reactive species in equilibrium with the starting material.…”