Synthesis, electrochemical, kinetic and thermodynamic properties of new ferrocene-containing betadiketonato rhodium(I) complexes with biomedical applications
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Date
2002-11
Authors
Klaas, Palesa
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Publisher
University of the Free State
Abstract
English: Synthetic routes to prepare new ferrocene-containing β-diketones, FcCOCH2COR, with Fc =
ferrocenyl, R = H, CH3, CH2CH3, CH(CH3)2 and C(CH3)3, have been developed. Rhodium
complexes of the type [Rh(FcCOCHCOR)(cod)] were obtained in yields approaching 80% by
treating these β-diketones with [Rh2Cl2-(cod)2]. Group electronegativities XR of R substituents were
determined from a linear relationship between ethyl ester IR carbonyl stretching frequencies of the
type RCOOCH2CH3 and group electronegativities of known R groups. pKa values of new β -diketones were determined. 1H NMR studies on FcCOCH2COR indicated that enolisation in the
direction furthest from the ferrocenyl group always dominate. This finding is considered to be the
result of resonance driving force rather than inductive electronic effects of substituents on the
pseudo-aromatic β-diketone core.
Formal reduction potentials (Eol values vs. Ag/Ag+) of the iron core in the free β-diketones,
FcCOCH2COR, and in [Rh(FcCOCHCOR)(cod)] complexes as well as the peak anodic oxidation
potentials, Epa, of the rhodium(I) nucleus were determined. The roles of pKa and group electronegativities on redox potentials are also discussed.
Second-order rate constants, k2, for the substitution of the β-diketonato ligand, (FcCOCHCOR),
from the complexes [Rh(FcCOCHCOR)(cod)] with 1,10-phenanthroline at 25°C in methanol were
determined. Large negative values obtained for entropy of activation suggested an associative
substitution mechanism. All substitution reactions were independent of a solvent step.
Cytotoxic properties in terms of potential anticancer applications of these newly synthesised β- diketones and their rhodium complexes on cancer cells are described. Cytotoxicity was tested on
HeLa, A2780 and A2780 platinum resistant cancer cells lines. Rhodium complexes were observed to
be more effective in killing cancer cells than the free β-diketones.
Afrikaans: Sintetiese prosedures ter bereiding van nuwe ferroseenbevattende β-diketone, FeCOCH2COR, met Fe = ferroseniel, R = H, CH3, CH2CH3, CH(CH3)2 en C(CH3)3, is ontwikkel. Rodiumkomplekse van die tipe [Rh(FeCOCHCOR)(eod)] in opbrengste van bykans 80% is verkry deur hierdie β-diketone met [Rh2Ch(eod)2] te reageer. Groep elektronegatiwiteite, XR, van die R-substituente is bepaal vanaf direkte verwantskappe tussen etielester IR.-karboniel strekkingsfrekwensies van die tipe RCOOCH2CH3 en groep elektronegatiwiteite van bekende R-groepe. pKa-waardes van nuwe β-diketone is bepaal. 1H KMR studies van FeCOCH2COR het deurgaans gedui op dominante enolisasie in die rigting verste van die ferroseniel groep. Hierdie bevinding word beskou as die resultaat van resonansdryfkragte eerder as induktiewe elektroniese effekte van substituente op die pseudo-aromatiese β-diketoon kern. Formele reduksiepotensiale (Eol waardes vs. Ag/Ag) van die yster kern in die vry β-diketone, FeCOCH2COR, en in [Rh(FeCOCHCOR)(cod)] komplekse, sowel as die piek anodiese oksidasiepotensiale, Epa, van rodium(I)kerne was bepaal. Die rol wat pKa en groep elektronegatiwiteite op redokspotensiale speel is ook bespreek. Tweede-orde tempokonstantes, k2, vir die substitusie van die β-diketonato ligand (FeCOCHCORr, van komplekse [Rh(FeCOCHCOR)(eod)] met 1,10-fenantrolien by 25°C in metanol was bepaal. Die groot negatiewe waardes wat verkry is vir die aktiveringsentropie dui op 'n assosiatiewe substitusie meganisme. Alle substitusiereaksies was onafhanklik van 'n oplosmiddel stap. Sitotoksiese eienskappe in terme van potensiële antikanker toepassings van hierdie nuut Gesintetiseerde β-diketone en hulle rodiumkomplekse op kankerselle is beskryf. Sitotoksisiteit op HeLa, A2780en A2780platinum weerstandbiedende kankerselbelynings is getoets. Daar is bevind dat rodiumkomplekse meer effektief is as β-diketone in die vernietiging van kankerselle.
Afrikaans: Sintetiese prosedures ter bereiding van nuwe ferroseenbevattende β-diketone, FeCOCH2COR, met Fe = ferroseniel, R = H, CH3, CH2CH3, CH(CH3)2 en C(CH3)3, is ontwikkel. Rodiumkomplekse van die tipe [Rh(FeCOCHCOR)(eod)] in opbrengste van bykans 80% is verkry deur hierdie β-diketone met [Rh2Ch(eod)2] te reageer. Groep elektronegatiwiteite, XR, van die R-substituente is bepaal vanaf direkte verwantskappe tussen etielester IR.-karboniel strekkingsfrekwensies van die tipe RCOOCH2CH3 en groep elektronegatiwiteite van bekende R-groepe. pKa-waardes van nuwe β-diketone is bepaal. 1H KMR studies van FeCOCH2COR het deurgaans gedui op dominante enolisasie in die rigting verste van die ferroseniel groep. Hierdie bevinding word beskou as die resultaat van resonansdryfkragte eerder as induktiewe elektroniese effekte van substituente op die pseudo-aromatiese β-diketoon kern. Formele reduksiepotensiale (Eol waardes vs. Ag/Ag) van die yster kern in die vry β-diketone, FeCOCH2COR, en in [Rh(FeCOCHCOR)(cod)] komplekse, sowel as die piek anodiese oksidasiepotensiale, Epa, van rodium(I)kerne was bepaal. Die rol wat pKa en groep elektronegatiwiteite op redokspotensiale speel is ook bespreek. Tweede-orde tempokonstantes, k2, vir die substitusie van die β-diketonato ligand (FeCOCHCORr, van komplekse [Rh(FeCOCHCOR)(eod)] met 1,10-fenantrolien by 25°C in metanol was bepaal. Die groot negatiewe waardes wat verkry is vir die aktiveringsentropie dui op 'n assosiatiewe substitusie meganisme. Alle substitusiereaksies was onafhanklik van 'n oplosmiddel stap. Sitotoksiese eienskappe in terme van potensiële antikanker toepassings van hierdie nuut Gesintetiseerde β-diketone en hulle rodiumkomplekse op kankerselle is beskryf. Sitotoksisiteit op HeLa, A2780en A2780platinum weerstandbiedende kankerselbelynings is getoets. Daar is bevind dat rodiumkomplekse meer effektief is as β-diketone in die vernietiging van kankerselle.
Description
Keywords
β-diketones, Rhodium, Group electronegativities, Cyclic voltammetry, Ferrocene, Substitution kinetics and cytotoxicity, Ligands, Complex compounds, Dissertation (M.Sc. (Chemistry))--University of the Free State, 2002