Resumen

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 (E_L) 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 (σ_r + σ_r,) - 2.24 (R² = 0.99) = 31.8 ΣE_l - 63.0 (R² = 0.99) = - 9.16 E_HOMO - 52.1 (R² = 0.97) = 101 ΣQ_Mulliken(Rh(CO)₂) - 49.9 (R² = 0.99).

Palabras clave : BETA-diketone; rhodium; substitution; dicarbonyl; cyclo-octadiene; DFT.

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