The reaction of the cis-dioxorhenium(V) core with <f>N</f>,<f>O</f>-donor ligands: mono and bidentate coordination of 3-methyl-2-aminophenol

The reaction of cis-[ReO2I(PPh3)2] with 3-methyl-2-aminophenol (H2map) in ethanol led to the formation of trans-[Re(map)(Hmap)I(PPh3)2]I. The X-ray crystal structure shows that the ligand map is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hmap is coordinated via the neutral amino nitrogen and the singly deprotonated phenolate oxygen, which is coordinated trans to the imido nitrogen. In benzene equimolar quantities of cis-[ReO2I(PPh3)2] and 4-methyl-2-aminophenol (H2amp) produced the five-coordinate cis-[ReO2(Hamp)(PPh3)]. A twofold molar excess of 2-aminophenol (H2ap) yielded the six-coordinate [ReO(Hap)(ap)(PPh3)]. The chelate ap is coordinated through the deprotonated phenolate oxygen and the singly deprotonated amino nitrogen (amide). [Copyright &y& Elsevier]