Abstract

A number of neutral and lipophilic oxo(L)technetium(V) complexes have been synthesized, where L is a tetradentate amine oxime for which 3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime (Pn(AO)/sub 2/) is the prototype. These TcOL complexes have been characterized by their visible-uv spectra, ir spectra, /sup 1/H and /sup 13/C NMR spectra, fast atom bombardment (FAB) mass spectra, and x-ray diffraction studies. The x-ray crystal structures of four of these complexes show them to be mono(oxo)technetium(V) species with the oxo group situated at the apex of a square pyramid and the technetium lying an average of 0.68 A above the plane defined by the four nitrogen atoms of the tetradentate amine oxime. In each case the tetradentate amine oxime ligand loses three protons on coordination to the technetium(V) center, resulting in an overall charge of zero for the complex, multiple bonding between the amide nitrogens and the technetium, and intramolecular hydrogen bonding between the oxime oxygens. The space constants are reported for the complexes.

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