학술논문
Synthesis of bis[palladium(ii)] and bis[platinum(ii)] complexes containing chiral, linear quadridentate ligands with a P2N2 donor set
Document Type
Article
Author
Source
Journal of the Chemical Society, Dalton Transactions; January 10, 2002, Vol. 2002 Issue: 2 p234-243, 10p
Subject
Language
ISSN
03009246
Abstract
A number of bis[palladium(ii)] and bis[platinum(ii)] complexes of the type [(MCl2)2(μ-quadridentate)] [where M = Pd(ii) or Pt(ii)] and [(PtClMe)2(μ-quadridentate)] have been prepared containing the linear quadridentate NPPN ligands 1,3-bis[(2-aminophenyl)phenylphosphino]propane, 1 ; 1,4-bis[(2-aminophenyl)phenylphosphino]butane, 2 ; 1,5-bis[(2-aminophenyl)phenylphosphino]pentane, 3 [Pd(ii) only]; 1,6-bis[(2-aminophenyl)phenylphosphino]hexane, 4 ; and 1,3-bis[(2-aminoethyl)phenylphosphino]propane, 5 ; and the related PNNP ligands 1,3-bis[(2-diphenylphosphinophenyl)amino]propane, 6 ; and 1,2-bis[(2-diphenylphosphinophenyl)amino]ethane, 7 [Pt(ii) only]. Separation of the racemic and meso diastereomers of the linear quadridentate NPPN ligands and the resolution of (RP*,RP*)-1 have been achieved via separation by fractional crystallisation of a pair of bis[palladium(ii)] complexes containing the respective ligand and orthometallated N,N-dimethylbenzylamine or (S)-dimethyl(1-phenylethyl)amine, respectively. The structure of the bis[palladium(ii)] complex containing (RP,RP)-1 has been confirmed by X-ray analysis and shown to have the configuration (SP,SP,S,S). Subsequent reaction of stereoisomerically pure [{Pd(2-C6H4CH2NMe2)}2(μ-L)](PF6)2 with HCl gave the corresponding complexes [(PdCl2)2(μ-L)] [where L = (RP*,RP*)-15 , (RP,RP)- or (SP,SP)-1 , (RP*,SP*)-1 , -2 or -5 ]. The analogous complex [(PdCl2)2(μ-6 )] has been prepared in a similar manner. Bis[platinum(ii)] complexes of the type [(PtClMe)2(μ-L)] [where L = (RP*,RP*)-1 , -2 or -4 ; (RP,RP)-, (SP,SP)- or (RP*,SP*)-1 ; 6 or 7 ] have been prepared by reaction of L with [PtCl(Me)(cod)] (cod = cyclocta-1,5-diene). Further treatment with HCl gave the analogous complexes [(PtCl2)2(μ-L)] [where L = (RP*,RP*)-1 , -2 , -4 or -5 ; (RP*,SP*)-1 or -5 ; or 6 ]. The dinuclear compounds and, in particular, the bis[platinum(ii)] complexes, are seen as potential anticancer agents. Preliminary in vitro biological studies have shown them to be active against the murine P388 leukaemia cell-line with cytotoxicities of certain of these complexes being comparable to that of cisplatin.