We have recently explored the hydrothermal preparation of low-valent Tc complexes.  In this talk, we present a series of technetium acetate paddle-wheel complexes capped with the halides Cl, Br, and I.  Two classes have been prepared: Tc2(O2CCH3)4X2 (X = Cl, Br, I) are halide-capped molecular complexes with quadruple bonds.  Tc2(O2CCH3)4X (X = Cl, Br, I) consist of infinite 1D chains where a single halide connects two paddlewheels.  The lower oxidation state leads to bond orders of 3.5 and a shorter metal-metal bond.  We show that these complexes are useful starting points for synthesis.  Heating Tc2(O2CCH3)4Cl2 in the presence of HCl gas leads to the formation of a Tc2(O2CCH3)2Cl4 intermediate followed, at higher temperatures, by the formation of TcCl3.  Characterization through single crystal X-ray diffraction, spectroscopy, and first-principles calculations are discussed. Keywords: technetium carboxylates; metal-metal bonds; metal-halogen bond; hydro/solvo-thermal reactions; characterization(SC-XRD, FTIR, UV-Vis).

Halide capped technetium acetate paddlewheel complexes with metal-metal bond orders higher than three

246th National Meeting (2013)

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