Monocapped tris(dioxime) complexes of technetium(III): Synthesis and structural characterization of TcX(dioxime) sub 3 B-R (X = Cl, Br; dioxime = dimethylglyoxime, cyclohexanedione dioxime; R = CH sub 3 , C sub 4 H sub 9 )

Monocapped boronic acid adducts of technetium tris(dioxime) complexes (BATO), TcX(dioximeH){sub 2}(dioxime)B-R, where X = Cl or Br, dioxime = cyclohexanedione dioxime or dimethylglyoxime, and R = methyl or butyl, have been prepared by template synthesis starting with pertechnetate and stannous ion, (N(C{sub 4}H{sub 9}){sub 4})(TcOCl{sub 4}), or M{sub 2}(TcX{sub 6}) (M = NH{sub 4}, K; X = Cl, Br). These seven-coordinate Tc(III) compounds are the first examples of tris(dioxime) complexes in which one and only one oxygen of each of the three dioximes is joined to a common cap atom (boron). The crystal structures of three of the BATO complexes have been determined and are reported. The three dioxime oxygens on the uncapped end of the molecule are intramolecularly hydrogen bonded to two bridging protons. A halogen occupies the seventh coordination site. 34 refs., 4 figs., 8 tabs.