Synthetic, electrochemical and structural aspects of a series of ferrocene-containing dicarbonyl β-diketonato rhodium(I) complexes

The Relationship between the Electrochemical and Chemical Oxidation of Ferrocene‐Containing Carbonyl‐Phosphane‐β‐Diketonato‐Rhodium(I) Complexes – Cytotoxicity of [Rh(FcCOCHCOPh)(CO)(PPh3)]

“…[16] The inequivalence of the ferrocenyl (Fc) and ferrocenium (Fc + ) groups of this intermediate is highlighted in terms of their group electronegativities: χ Fc = 1.87, χ Fc+ = 2.82. [9,13,17] The electron-withdrawing power of the ferrocenium group is almost as high as that of the CF 3 group (χ CF3 = 3.01). As there is good communication (by conjuga- ΔE p /mV…”

Reactivity of [Rh(β-diketonato)(cod)] complexes: A DFT approach

“…The substitution reaction of 1,10-phenanthroline for b-diketonato ligand from [Rh(R 0 COCHCOR)(cod)] (Scheme 1 reaction 5) is proposed to proceed through an associative mechanism involving the formation of a five-coordinate species followed by breakage of one of the two oxygeneRh bonds of the b-diketonato coordinated to the rhodium nucleus [16]. The Frontier Molecular Orbital Theory (FMO Theory) simplifies reactivity to interactions between the HOMO of one species and the LUMO of the other [37].…”

“…These complexes can undergo a variety of substitutions, see Scheme 1 for selected reactions. For example: cod in [Rh(b-diketonato)(cod)] (cod ¼ 1,5-cyclooctadiene) can be replaced by two monodentate carbon monoxide ligands [16,17] (Scheme 1 reaction 1) or by two phosphite groups [18,19] (Scheme 1 reaction 2). Triphenyl phosphine can only substitute one CO in [Rh(b-diketonato)(CO) 2 ] [20] (Scheme 1 reaction 3) while triphenyl phosphite substitutes both CO groups [19,21] (Scheme 1 reaction 4).…”

Prediction of chemical and electrochemical oxidation potentials of β-diketonatobis(triphenylphosphite)rhodium(I) complexes: A DFT study

“…Various parameters can be used to describe the electronic effect of the substituent groups R and R 0 of which the pK a of the free b-diketone and the Gordy scale group electronegativities (v R + v R 0 ) are often used [21,22,[37][38][39][40][41][42].…”