Peripherally Metallated Porphyrins: the First Examples of Meso-n1-Palladio(II) and -Platinio(II) Complexes with Chelating Diamine Ligands

The oxidative addition of bis(dibenzylideneacetone)platinum(0) to meso-bromo-5,15-diarylporphyrins in the presence of PPh3 has been shown to be an effective way of synthesising η1-organoplatinum porphyrins in high yields. This methodology has been extended to synthesise various palladio- and platinioporphyrins that utilise bidentate nitrogen donor ligands [N,N,N’,N’-tetramethylethylenediamine (tmeda) and 2,2’-bipyridyl (bpy)] in order to enforce a cis configuration at the metal centre. The products were characterised by multinuclear NMR and UV-visible spectroscopies as well as fast atom bombardment and high-resolution electrospray ionisation mass spectrometries