24151-55-1Relevant academic research and scientific papers
Chemical and electrochemical oxidation of [Rh(β-diketonato)(CO) (P(OCH2)3CCH3)]: An experimental and DFT study
Erasmus, Johannes J. C.,Conradie, Jeanet
, p. 8655 - 8666 (2013)
An experimental and computational chemistry study of the reactivity of [Rh(β-diketonato)(CO)(P(OCH2)3CCH3)] complexes towards chemical and electrochemical oxidation shows that more electron withdrawing groups on the β-diketonato ligand reduce electron density on the rhodium atom to a larger extent than electron donating groups. This leads to a slower second-order oxidative addition rate, k1, and a higher electrochemical oxidation potential, Epa(Rh), linearly related by ln k1 = -11(1) Epa(Rh) - 2.3(5). The reactivity of these complexes can be predicted by their DFT calculated HOMO energies: EHOMO = -0.34(8)Epa(Rh) - 5.04(4) = 0.032(5) ln k 1 - 4.96(4). k1 of [Rh(β-diketonato)(CO)(P(OCH 2)3CCH3)] complexes is slower than that of related [Rh(β-diketonato)(CO)(PPh3)] and [Rh(β-diketonato) (P(OPh)3)2] complexes due to the better π-acceptor ability of the CO-phosphite-rhodium combination than that of CO-PPh 3-rhodium or di-phosphite-rhodium.
