Syntheses and Structures of Tris-(1,2-Benzosemiquinone DIimine) Complexes of Rhenium(IV)

Reactions of trans-[ReO 2 (py) 4 Cl] and cis-[ReO 2 I(PPh 3 ) 2 ] with 2,3-diaminophenol (H 2 dab-OH) and 1,2-diaminobenzene (H 2 dab), 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...

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Bibliographic Details
Published in:Journal of coordination chemistry 2003-08, Vol.56 (12), p.1049-1061
Main Authors: Gerber, T. I. A., Luzipo, D., Mayer, P., Van Brecht, B. J. A. M., Du Preez, J. G. H.
Format: Article
Language:English
Subjects:
Crystal Structure
Rhenium(IV)
Semiquinone Diimine
π-Radical
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Summary:Reactions of trans-[ReO 2 (py) 4 Cl] and cis-[ReO 2 I(PPh 3 ) 2 ] with 2,3-diaminophenol (H 2 dab-OH) and 1,2-diaminobenzene (H 2 dab), 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 H 2 dab. 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.
ISSN:0095-8972
1029-0389
DOI:10.1080/00958970310001596764