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Multidentate phosphinimine ligands, C25H49N2P2Si2,(2) C34H38N2P2Si2(3), and C50H66N3P3Si3(4), were synthesized in near quantitative yields by Staudinger reaction using appropriate phosphines. Coordination chemistry of 2 and 3 with Re was performed and the X-ray crystallographic study of the Re ion-pair complex of ligand 2 is reported. Radiolabeling of ligands 2, 3 and 4 with Tc was performed. Simple mixing of ligand solutions with aqueous TcO4 in saline solution produced ion-pairs with more than 95% yields. All three ion-pairs produced are stable for more than 24 h in organic media and in alcohols. The ion-pair produced with ligand 3 ([(NH2PPh2CH2PPh2NH or O) (TcO4)] ), upon heating has resulted in the neutral complex [(NH2PPh2CH2PPh2NH or O) (TcO3)]. Upon heating the ion-pair ([(NH2PPh2CH2PPh2NH) (ReO4)] in the presence of Verkade’s superbase led to the rearrangement of the ligand via cleavage of the P-C-P bridge to produce P-N-P bridged compound.

Synthesis and characterization of novel phosphinimine ligand systems for potential applications in radiopharmaceuticals