From TcVII to TcI; facile syntheses of bis-arene complexes [99(m)Tc(arene)2]+ from pertechnetate† †Electronic supplementary information (ESI) available: Additional synthetic and characterization details (including HPLC, NMR, CV), and crystallographic details. CCDC 1017765, 1017766, 1017767, 1017768 and 1017769. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02461c Click here for additional data file. Click here for additional data file.

Bis-arene complexes of technetium represent a fundamental class of organometallic compounds. Due to complex synthetic routes, no detailed insights into their properties have been reported so far. Reacting [TcO4] with arenes in the exclusive presence of AlCl3 gives highly stable [ Tc(arene)2] + in good yields. These complexes have extraordinarily high stabilities, where oxidation is found to occur at potentials higher than +1.3 V and reduction at potentials below 2 V vs. Fc/Fc. The Tc analogues are similarly synthesised by applying a novel ionic liquid extraction pathway. Complexes of Tc with suitably functionalized arenes will represent new building blocks for bioorganometallic pharmaceuticals in molecular imaging.