Abstract
The second order rate constants, k2, for the displacement of chloride by nitrogen donors L (L = thiazoles, pyridines, amines) from [Pt(S-S)Cl2] [S-S = 1, 2-bis-(phenylsulfanyl) ethane] and [Pt(SNS)Cl]+ [SNS=2, 6-bis- (methylsulfanylmethyl)pyridine] are linearly related to their proton basicity according to a free-energy relationship of the type logk2 = α(pKa) + β. In the reverse reactions, i.e. the displacement by chloride of the coordinated nitrogen donors, the lability depends not only upon ligand basicity but also upon the nature of the group to be displaced in the order thiazoles < pyridines. This behaviour, attributed to different π interactions in the ground state, is confirmed in the solvolytic displacement of the organic bases from complexes of the type trans-[Pt(dmso)(L)Cl2]. Steric retardation, owing to the presence of a methyl group ortho to the nitrogen in the aromatic rings, is considerably less for entering thiazoles as compared to pyridines.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
