Transition metal complexes of rhenium and technetium find wide application in nuclear medicine and the chemistry of these elements is still the focus of intense research efforts. For therapeutic and diagnostic applications, currently much attention is dedicated to the development of new targeting strategies aimed at appending the metal complexes to biological vectors (e.g. a peptide) for a site-specific delivery of the radionuclides. Advancements in radiopharmacy, however, will not only arise from the development of new targeted strategies but also from the exploration of the chemistry of these elements in their unusual oxidation states. In this respect the even number oxidation states of Re and Tc (i.e. +II, +IV and +VI) are relatively poorly understood. In particular, stable and substitutionally labile mononuclear 17-electron species of the elements (+II, d(5)) are a rarely encountered class of complexes. In this review we present our recent developments in the field of rhenium (II) chemistry with emphasis on the novel synthetic strategies we have recently introduced. We will also describe how the unique chemical and electronic properties of Re(II)-based complexes may provide a potentially new approach for applications in inorganic medicinal chemistry.