Cationic five-coordinate PtII complexes as donors in the formation of Pt→Ag dative bonds

A unique trinuclear cluster containing two short Pt -> Ag dative bonds was prepared and characterized crystallographically. Two monocationic orthometalated Pt-II complexes containing 2-phenylpyridine and the tridentate ligand 9S3 (1,4,7-trithiacyclononane) exhibit axial sulfur interactions with Pt as well as short dative bonds. The Pt -> Ag dative bonding results in a dramatic shortening of the axial Pt-S distance in each Pt complex cation, relative to the mononuclear Pt complex. Evidence for Pt-Ag interactions in solution is also presented.