N-Centered Tripodal Phosphine Re(V) and Tc(V) Oxo Complexes: Revisiting a [3 + 2] Mixed-Ligand Approach

N-Triphos derivatives (NP 3 R , R = alkyl, aryl) and asymmetric variants (NP 2 R X R' , R' = alkyl, aryl, X = OH, NR 2 , NRR') are an underexplored class of tuneable, tripodal ligands in relation to the coordination chemistry of Re and Tc for biomedical applications. Mixed-ligand approaches are a flexible synthetic route to obtain Tc complexes of differing core structures and physicochemical properties. Reaction of the NP 3 Ph ligand with the Re(V) oxo precursor [ReOCl 3 (PPh 3 ) 2 ] generated the bidentate complex [ReOCl 3 (κ 2 -NP 2 Ph OH Ar )], which possesses an unusual AA'BB'XX' spin system with a characteristic second-order NMR lineshape that is sensitive to the bi- or tridentate nature of the coordinating diphosphine unit. The use of the asymmetric NP 2 Ph OH Ar ligand resulted in the formation of both bidentate and tridentate products depending on the presence of base. The tridentate Re(V) complex [ReOCl 2 (κ 3 -NP 2 Ph O Ar )] has provided the basis of a new reactive "metal-fragment" for further functionalization in [3 + 2] mixed-ligand complexes. The synthesis of [3 + 2] complexes with catechol-based π-donors could also be achieved under one-pot, single-step conditions from Re(V) oxo precursors. Analogous complexes can also be synthesized from suitable 99 Tc(V) precursors, and these complexes have been shown to exhibit highly similar structural properties through spectroscopic and chromatographic analysis. However, a tendency for the {M V O} 3+ core to undergo hydrolysis to the {M V O 2 } + core has been observed both in the case of M = Re and markedly for M = 99 Tc complexes. It is likely that controlling this pathway will be critical to the generation of further stable Tc(V) derivatives.