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The versatility of aniline derivatives as ligands for Re(V) and Tc(V) has been investigated. The reaction of (nBu4N) [MOC14] (M=Re, Tc) with 1,2-diaminobenzene (H2dab) and 2,3-diaminopyridine (H2dap) gave the products (Bu4N)[MO(dab)2] (1) and [MO(dapH)2]Cl (2) respectively. Both chelates in 1 and 2 are coordinated as diamides; however, in 2 the pyridine nitrogens of dapH are protonated. With traps-[ReOCl3(PPh3)2] as a starting complex, a number of products were isolated, depending on the reaction conditions. For example, with 3-hydroxy-l,2-diaminobenzene (H2dab-OH) under N2, [Re(dab-OH)Cl3(PPh3)2] (3) was produced, in which dab-OH substituted the oxo group and is coordinated as a monodentate imide. With 3-nitro-l,2-diaminobenzene (H2dab-NO2), the oxo-free complex [ReCl(PPh3)(dab-NO2)2] (4) was obtained, with bidentate diamido coordination of each chelate. Using trans[ReO2(py)4]Cl as a starting complex, complexes of the type [Re(sbgdi-OH)3]Cl (5) and cis-[ReO2(Hdab)(py)2] (6) were isolated, where sbqdi-OH coordinates as the monoanionic semibenzoquinonediimine and Hdab as a bidentate monoamide. The crystal structures of these complexes are discussed in this account.

Versatility of Bidentate Aniline Derivatives as Ligands for Rhenium (V) and Technetium (V)