Experimental and Theoretical Studies of the Factors Affecting the Cycloplatination of the Chiral Ferrocenylaldimine (SC)-[(η5-C5H5)Fe{(η5-C5H4)–C(H)=N–CH(Me)(C6H5)}]

Inorganics

Concepción López¹  Ramón Bosque¹  Marta Pujol¹  Jonathan Simó¹  Eila Sevilla¹  Mercè Font-Bard໚³  Ramon Messeguer²  Carme Calvis² 

[1]Departament de Química Inorgánica, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11. E-08028 Barcelona, Spain

[2] E-Mails:

[3]Biomed Division, Leitat Tecnological Center, Parc Científic de Barcelona, Edifici Hèlix, C/Baldiri i Reixach, 15-21, E-08028 Barcelona, Spain

[4] E-Mails:

[5]Unitat de Difracció de Raigs-X, Centre Científic i Tecnològic de la Universitat de Barcelona, Solé i Sabarís 1-3, E-08028 Barcelona, Spain

[6] E-Mail:

关键词: platinacycles;    chiral platinum(II) complexes;    DFT calculations;    biological activity;    electrochemistry;   

DOI  :  10.3390/inorganics2040620

来源: mdpi

【 摘 要 】

The study of the reactivity of the enantiopure ferrocenyl Schiff base (S_C)-[FcCH=N–CH(Me)(C₆H₅)] (1) (Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)) with cis-[PtCl₂(dmso)₂] under different experimental conditions is reported. Four different types of chiral Pt(II) have been isolated and characterized. One of them is the enantiomerically pure trans-(S_C)-[Pt{κ¹-N[FcCH=N–CH(Me)(C₆H₅)]}Cl₂(dmso)] (2a) in which the imine acts as a neutral N-donor ligand; while the other three are the cycloplatinated complexes: [Pt{κ²-C,N[(C₆H₄)–N=CHFc]}Cl(dmso)] (7a) and the two diastereomers {(S_p,S_C) and (R_p,S_C)} of [Pt{κ²-C,N[(η⁵-C₅H₃)–CH=N–{CH(Me)(C₆H₅)}]Fe(η⁵-C₅H₅)}Cl(dmso)] (8a and 9a, respectively). Isomers 7a-9a, differ in the nature of the metallated carbon atom [C^Ph (in 7a) or C^Fc (in 8a and 9a)] or the planar chirality of the 1,2-disubstituted ferrocenyl unit (8a and 9a). Reactions of 7a–9a with PPh₃ gave [Pt{κ²-C,N[(C₆H₄)–N=CHFc]}Cl(PPh₃)] (in 7b) and the diastereomers (S_p,S_C) and (R_p,S_C) of [Pt{κ²-C,N[(η⁵-C₅H₃)–CH=N–{CH(Me)(C₆H₅)}] Fe(η⁵-C₅H₅)}Cl(PPh₃)] (8b and 9b, respectively). Comparative studies of the electrochemical properties and cytotoxic activities on MCF7 and MDA-MB231 breast cancer cell lines of 2a and cycloplatinated complexes 7b-9b are also reported. Theoretical studies based on DFT calculations have also been carried out in order to rationalize the results obtained from the cycloplatination of 1, the stability of the Pt(II) complexes and their electrochemical properties.

【 授权许可】

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