Syntheses and structural characterization of rhenium-bis-hydrazinopyrimidine core complexes with thiolate and Schiff base coligands

The reaction of perrhenate with 2-hydrazinopyrimidine in MeOH–HCl yields [ReCl3(η1-NNC4H3N2H)(η2-HNNC4H3N2)] (1). The analogous reaction with Na2MoO4 yields [MoCl3(η1-NNC4H3N2H)(η2-HNNHC4H3N2)] (1a). The reaction of 1 with pyrimidine-2-thiol and triethylamine produces [Re(η1-C4H3N2S)(η2-C4H3N2S)(η1-NNC4H3N2)(η2-HNNC4H3N2)] (2), while reaction of 1 with the Schiff base HSC6H4NC(H)C6H4OH provides [Re(η3-SC6H4NC(H)C6H4O)(η1-NNC4H3N2)(η2-HNNC4H3N2)]·0.6CH2Cl2 (3·0.6CH2Cl2). The analogous hydrazinopyridine complex of the Schiff base, [Re(η3-SC6H4NC(H)C6H4O)(η1-NNC5H4N)(η2-HNNC5H4N)] (4), was also synthesized by reacting [ReCl3(η1-NNC5H4NH)(η2-HNNC5H4N)] with HSC6H4NC(H)C6H4OH. The crystal structures of 1–4 have been determined.