Synthesis and characterization of oxorhenium(V)-catecholate complexes. Crystal and molecular structures of (CH3)4N[ReO (O2C6H4)2] and (CH3)4N[ReO(PPh3) (O2C6H4)2]·CH3OH

Peter B. Kettler, Chang Yuan-Da, Jon Zubieta, Michael J. Abrams

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

The reactions of ReOCl3(PPh3)2 with catechol and substituted catechols in methanol in the presence of triethylamine and tetramethylammonium chloride under N2 yield the green complexes [(CH3)4N]+[ReO(cat)2(PPh3)]- (cat=O2C6H4 (2), 4CH3O2C6H3 (3), O2C6Cl4 (4)). The reactions of 2 and 3 with pyridine in methylene chloride yield [(CH3)4N]+[ReO(cat)2(py)]- (5) and [(CH3)4N]+[ReO(4Mecat)2(py)]- (6). Variable temperature 1H and 31P NMR spectroscopy studies on these complexes indicate that the ancillary ligands (PPh3: 2, 3; py: 5, 6) undergo a dissociation-association process in solution along with concomitant cis-trans isomerization of the catecholate ligands. The reaction of [(CH3CH2)4N]+[ReO2(cat)2]- (8) with triphenylphosphine in refluxing ethanol yields the reduced rhenium(V) square pyramidal complex [(CH3CH2)4N]+[ReO(cat)2]- (7) as an air and moisture-sensitive tan solid where triphenylphosphine acts as a reducing agent. These complexes were characterized by elemental analysis, variable temperature 1H and 31P NMR spectroscopy and IR and UV-Vis spectroscopies. Complexes 2 and 7 were also characterized by X-ray crystallography. Crystal data: C20H28NO5Re (2): tetragonal space group I4/m, a=19.890(3), c=10.438(2) Å, V=4129(2) Å3, Z=8, Dcalc=1.766 g cm-3; structure solution and refinement based on 976 reflections (Mo Kα, λ=0.71073 Å) converged at R=0.043. C36H43NO7PPe (7): monoclinic space group C2/c, a=25.485(5) Å, b=9.127(2), c=30.590(6) Å, β=101.84(3)°, V=6964(3) Å3, Z=8, Dcalc=1.563 g cm-3; 3298 reflections, R=0.047.

Original languageEnglish (US)
Pages (from-to)157-165
Number of pages9
JournalInorganica Chimica Acta
Volume218
Issue number1-2
DOIs
StatePublished - Apr 1994

Keywords

  • Catecholate complexes
  • Crystal structures
  • Oxo complexes
  • Rhenium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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