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 journalArticle

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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