South African Journal of Chemistry
versão On-line ISSN 1996-840X
CONRADIE, Jeanet. Carbonyl substitution in β-diketonatodicarbonyl-rhodium(I) by cyclo-octadiene: Relationships with experimental, electronic and calculated parameters. S.Afr.j.chem. (Online) [online]. 2013, vol.66, pp. 00-00. ISSN 1996-840X.
The substitution rate constant of the reaction between [Rh(β-diketonato)(CO)2] and cyclo-octadiene is related to various empirical parameters and density functional theory calculated energies and charges, β-diketonato = R'COCHCOR. Results indicate that especially the Hammett meta substituent constants (σ), the Lever electronic parameters (EL) and the density functional theory calculated energies and charges predict the substitution rate constant to a high degree of accuracy, for example: ln k2 = 8.48 (σr + σr,) - 2.24 (R2 = 0.99) = 31.8 ΣEl - 63.0 (R2 = 0.99) = - 9.16 EHOMO - 52.1 (R2 = 0.97) = 101 ΣQMulliken(Rh(CO)2) - 49.9 (R2 = 0.99).
Palavras-chave : BETA-diketone; rhodium; substitution; dicarbonyl; cyclo-octadiene; DFT.