Attachment of a thioamide tethering group provides a modification of the well-known pyridylhydrazine based route to radiolabelling of biomolecules (the HYNIC system) and gives a proligand which gives stable, well-defined chelated derivatives with both Re(v) oxo and Re(III) diazenide cores. Both display previously unknown bonding modes for the pyridylthiocarbazide ligands.