Monooxo complexes of rhenium(V) with 2-aminophenol and some of its derivatives (H(2)nod), containing the N,O donor-atom set, have been synthesized. Square-pyramidal complexes [ReO(nod)(2)](-) were isolated by reaction with (n-Bu4N) [ReOCl4] in ethanol. In benzene the neutral species [ReOCL(Hnod)(2)] were obtained. In the presence of hydrochloric acid in ethanol, the anionic complexes (n-Bu4N) [ReOCl3(Hnod)] were produced. Trans-[ReOCl3(PPh3)(2)] was also reacted with some of the H(2)nod ligands to yield [ReOCL2(Hnod)(PPh3)]. The crystal structure of [ReOCl2(Hmap)(PPh3)] (H(2)map=2-aminobenzylalcohol) was determined; crystals are monoclinic, P2(1)/n, with a=15.065(6), b=11.253(7), c=15.850(7)Angstrom, beta=94.27(4)degrees, U=2680(2)Angstrom(3) and Z=4. The structure was solved by the Patterson method and refined by full-matrix least-squares techniques to R=0.042. The monoanionic Hmap(-) ligand is coordinated as a bidentate through a neutral amino nitrogen and an anionic alcoholate oxygen atom, with the latter trans to the oxo group.