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

N-Triphos derivatives (NP₃^R, R = alkyl, aryl) and asymmetric variants (NP₂^RX^R', R' = alkyl, aryl, X = OH, NR₂, 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 NP₃^Ph ligand with the Re(V) oxo precursor [ReOCl₃(PPh₃)₂] generated the bidentate complex [ReOCl₃(κ²-NP₂^PhOH^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 NP₂^PhOH^Ar ligand resulted in the formation of both bidentate and tridentate products depending on the presence of base. The tridentate Re(V) complex [ReOCl₂(κ³-NP₂^PhO^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 ⁹⁹Tc(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^VO}³⁺ core to undergo hydrolysis to the {M^VO₂}⁺ core has been observed both in the case of M = Re and markedly for M = ⁹⁹Tc complexes. It is likely that controlling this pathway will be critical to the generation of further stable Tc(V) derivatives.