Multinuclear NMR Studies of Ligand-Exchange Reactions on Analogous Technetium(V) and Rhenium(V) Complexes. Relevance to nuclear medicine

The kinetics of pyridine exchange on trans-[MO₂(py)₄]⁺ have been followed by ¹H-NMR in CD₃NO₂ for M = Re, Tc: k²⁹⁸S^?1 = (5.5 ± 0.1) × 10^?6, 0.04 ± 0.02; ΔH^≠/kJmol^?1 = 111 ± 3, 101 ± 9; ΔS^≠/JK^?1mol^?1 = +28 ± 10, +68 ± 35. For the Re^v complex, pyridine and oxygen exchanges have been measured simultaneously by ¹H- and ¹⁷O-NMR in deuterated water: k²⁹⁸/s^?1 = (8.6 ± 0.2) × 10^?6 (py), (14.5 ± 0.3) × 10^?6 (oxygen); ΔH^≠/kJmol^?1 = 111 ± 1, 91 ± 1; ΔS /JK^?1mol^?1 = +32 ± 3, ?32 ± 4. For both complexes, the rate law for pyridine exchange is first-order in complex and zero-order in pyridine; together with the activation parameter values, and the fact that the rate does not depend significantly on the nature of the solvent, this strongly implies the operation of a dissociative mechanism. The ratio of pyridine exchange rates for the Tc and Re complexes at room temperature is ca. 8000. The consequences of these observations for radiopharmaceutical synthesis are discussed.