The syntheses and structures of '3 + 2' and '2 + 2 + 1' oxorhenium mixed-ligand complexes employing 8-hydroxy-5-nitroquinoline as the bidentate N,O donor ligand

Xiaoyuan Chen, Frank J. Femia, John W. Babich, Jon A Zubieta

Research output: Contribution to journalArticle

55 Scopus citations

Abstract

The syntheses and structural characterizations of a series of novel '3 + 2' and '2 + 2 + 1' mixed-ligand complexes carrying 8-hydroxy-5-nitroquinoline (HL) as the bidentate N,O donor atom system are reported. Thus, one-pot reactions of [ReOCl3(PPh3)2] with dianionic tridentate ligands H2L(n) (where H2L1 =HOC6H4-2-CH=NC6H4-2-OH; H2L2=HOC6H4-2-CH=N-C6H4-2-SH; H2L3 = HOC6H4-2-CH=NN=C(NHC6H5)-SH; H2L4 = 2-CH2OH-C5H3N-6-CH2SH; and H2L5 = 2-CO2H-C5H3N-6-CO2H) and HL afforded a series of '3 + 2' oxorhenium complexes of the type [ReO(H2L(n))(L)] 2-6, which exhibit distorted octahedral geometries. Crystals of 1 are monoclinic, space group C2/c, a = 16.702(1), b = 14.275(1), c = 22.363(2) Å, β = 108.083(1)°, V = 5068.2(7) Å3 and Z = 8; those of 2 are monoclinic, space group P21/n, a = 8.5093(4), b = 38.518(2), c = 11.6092(5) Å, β = 97.708(1)°, V = 3770.7(3) Å3 and Z = 8; those of 5 are triclinic, space group P1̄, a = 7.5899(8), b = 10.322(1), c=11.905(1) Å, α=78.636(2)°, β=74.229(2)°, γ=71.391(2)°, V=844.3(2) Å3, and Z=2. Upon reaction of 2,6-pyridinedimethanol (H2L6) with the intermediate complex [ReOCl2(L)(PPh3)] (1), only one of the two methylene hydroxy group was deprotonated and a new '2 + 2 + 1' complex [ReO(OCH3)(HL6)(L)]·CH3OH (7) was obtained. Crystal data for 7: monoclinic, P21/n, a = 12.0579(6), b = 11.0993(6), c = 14.9262(8) Å, β = 107.872(1)°, V = 1901.2(2) Å3, and Z = 8. In the preparation of complex 3, cleavage of the C=N bond of the Schiff base H2L2 was observed, and the '2 + 2 + 1' complex 8 [ReO(PPh3)(η2-NHC6H4-2-S)(L)]·CH2Cl2 having 2-aminothiophenol as a dianionic bidentate ligand was isolated. Crystals of 8 are monoclinic, space group C2/c, a = 25.627(2), b = 8.1305(6), c = 31.404(2) Å, β = 96.147(1)°, V= 6505.7(8) Å3, and Z = 8. Reduction of HL to 8-hydroxy-5-aminoquinoline was realized during the formation of complex 6, and a new complex 9 was thus isolated involving the coordination of two sets of N,O donor atoms from L and 8-hydroxy-5-aminoquinoline, while a methoxy oxygen atom completes the octahedral coordination geometry. Crystals of 9 are monoclinic, space group P21/n, a = 7.5330(6), b = 15.095(1), c = 16.394(1) Å, β = 99.690(2)°, V = 1837.7(3) Å3, and Z = 4. (C) 2000 Elsevier Science S.A.

Original languageEnglish (US)
Pages (from-to)80-90
Number of pages11
JournalInorganica Chimica Acta
Volume308
Issue number1-2
DOIs
StatePublished - Oct 20 2000

    Fingerprint

Keywords

  • Crystal structures
  • N,O donor ligand complexes
  • Oxo complexes
  • Rhenium complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this