Rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-decanyloxybenzoate: A DFT study of oxidative addition and methyl migration

Abstract

A density functional theory (DFT) study of the oxidative addition of iodomethane to a [Rh(β-diketonato)(CO)(PPh3)] complex containing a β-diketonato ligand, β-L1 = (CH3COC(C10H21OC6H4COO)COCH3)─, with a long chain (R3 = C10H21OC6H4COO) substituted at the C3 position of the β-diketonato ligand, is presented and compared to the oxidative addition of iodomethane to the mother compound [Rh(acac)(CO)(PPh3)], acac = (CH3COCHCOCH3)─, with a H at the C3 position The oxidative addition of iodomethane to both compounds follows a similar mechanism to form the first Rh(III)-alkyl1 product with methyl and iodide in the positions below and above the square plane formed by the CCO, PPPh3 and the two β-diketonato oxygens (Oβ). The follow-up carbonyl insertion and deinsertion steps, however, follow a different mechanism to from the second experimentally observed Rh(III)-alkyl2 product.