Abstract
Reactions of trans-[ReO2(py)4Cl] and cis-[ReO2I(PPh3)2] with 2,3-diaminophenol (H2dab-OH) and 1,2-diaminobenzene (H2dab), respectively, in ethanol under aerobic conditions led to the corresponding isolation of [Re(sbqdi-OH)3]Cl (1) and [Re(sbqdi)3]I (2). Crystallographic data show that the ligand sbqdi represents the monoanionic N,N-coordinated π-radical form of the 1,2-benzosemiquinone diimine of H2dab. The ligands in Complex 1 clearly show semiquinoid character; e.g., the two C-N and two Re-N bondlengths differ considerably. In 2, the phenyl rings display typical quinoid distortions with two localized double bonds, and the C-N bondlengths are short, approaching double bonds. Rhenium is formally in the +IV oxidation state.
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