Kinetics of substitution of ferrocenyl-containing β-diketonato ligands by phenanthroline from β-diketonato-1,5-cyclooctadienerhodium(I) complexes

Synthesis and electrochemical investigation of chromium(0) ferrocenyl-substituted carbene complexes

“…The electron-donating [8] characteristics of the ferrocenyl group, the electron-withdrawing properties of the oxidized ferrocenium species [9], the high thermal stability of both the oxidized and reduced states, and the electrochemical reversible nature of the Fc/Fc + couple [10] are but some of the reasons why ferrocene derivatives have been studied as molecular sensors [11] and in energy transfer processes [12]. Considering reaction rates, as a part of a ligand system it will enhance oxidative addition reactions [13] but retard substitution processes [14]. A particularly interesting application of ferrocene derivatives, which are strongly dependent on fine tuning of the ferrocenyl oxidation potential with suitable substituents, lies in the field of cancer therapy [15].…”

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

“…Experimentally it was found that the kinetic rate constant of the substitution reaction [Rh(R 0 COCHCOR)(cod)] þ phen / [Rh(phen)(cod)] þ þ (R 0 COCHCOR) À can be related to the pK a of the free of b-diketone (R 0 COCH 2 COR) [23] and the electronegativity of R and R 0 [24]. It was also found that the effect of the substituents R and R 0 on the reactivity of [Rh(R 0 COCHCOR)(CO) 2 ] towards substitution of the carbonyl groups(s) is of the same order of magnitude found for the substitution of phen for (R 0 COCHCOR) À from [Rh(R 0 COCHCOR)(cod)] complexes [23].…”

“…In view of the large influence of the electron donating or withdrawing properties of R and R 0 on the substitution reactivity of [Rh(R 0 COCHCOR)(cod)] complexes [23,24], we hereby present a DFT computational chemistry study of a series of eleven different [Rh(R 0 COCHCOR)(cod)] complexes (see Scheme 2) in search of a theoretical way of predicting reactivity.…”

Bis(1-ferrocenylbutane-1,3-dionato-κ2O,O′)copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-κ2O,O′)copper(II)

“…The 1,3--diketones 1-ferrocenylbutane-1,3-dione (HL 1 ; Fc-COCH 2 COCH 3 ; Cain et al 1961;Hennig & Gurtler, 1968;Bell et al, 1992;Zakaria et al;1995) and 1,3-diferrocenylpropane-1,3-dione (HL 2 ; FcCOCH 2 COFc; Woisetschlager et al, 1999;du Plessis et al, 1998du Plessis et al, , 2001) form coordination (Zanello et al, 1998;Che et al, 1998;Li et al, 2002) and organometallic complexes of interest in catalysis (Abiko & Wang, 1996Cullen et al, 1991;Swarts et al, 1993;Woisetschlager et al, 2000;Vosloo et al, 2002;Conradie et al, 2005).…”