ABSTRACT
We are interested in identifying mononuclear cationic [M(V)=O]3+ (M = Tc, Re) complexes for radiopharmaceutical applications. The open-chain ligand, 1,4,8,11-tetraazaundecane-5,7-dione-(dioxo-tetH6) with two amine and two amide donors, was selected for investigation since the literature led us to expect that a five-coordinate [Re(V)=O(dioxo-tetH4)]+ cation would dominate. Instead, the neutral mu-oxo bridged dinuclear complex, Re2O3(dioxo-tetH4)2 (1), and a salt of the six-coordinate mononuclear cation, [ReO(H2O)(dioxo-tetH4)]+ (2), were isolated; the structure of each was determined by X-ray crystallography. The cation (2) is unusual because it has a trans-oxo/aqua core. Such aqua compounds are rarely isolated, and the Re-OH2 distance is relatively short (2.185 A). The cation has two pKa values, 4.1 and 8.7, determined with visible spectroscopy. Since the Re-OH2 bond is short, the coordinated water is likely to be acidic. Thus the two pKa's are assigned to the stepwise deprotonation of the water ligand to give a trans-oxo/hydroxo neutral form and a trans-dioxo anion. Although 1 was the first product isolated following ligand exchange of ReOCl3(Me2S)(OPPh3) with dioxo-tetH6 under neutral conditions, it probably formed from the hydroxo mononuclear complex. Under concentrated conditions (approximately 300 mM) the dinuclear complex deposited from solution, but the 1H NMR spectra of 2 (approximately 20 mM) were consistent with the presence of only monomeric forms in D2O, pH 3-12. 1H NMR experiments demonstrated that in DMSO-d6 2 converts to 1 upon addition of base, consistent with the proposal that two units of the hydroxo monomer condense to give the dinuclear form. In addition, all spectra of pure 1 dissolved in DMSO-d6 included extra low intensity signals that were characteristic of the monomer. Thus, although 1 is favored over the neutral monomer in DMSO-d6, the two complexes exist as a mixture of equilibrating forms. Our results do not support the previous findings for the Re(V) complex with a macrocyclic diamine-diamide ligand related to dioxo-tetH6. The data indicate that the ability of an amido group to donate electron density to a Re(V) center is moderately greater than the donating ability of a neutral amine group.
