Osmium¯azopyrimidine chemistry. Part VII: synthesis, structural characterisation and electrochemistry

S Senapoti, US Ray, PK Santra, C Sinha, Alexandra Martha Zoya Slawin, John Derek Woollins

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)

Abstract

Reaction of 2-(arylazo)pyrimidines (R-C6H4-N=N-C4H3N2, abbreviated aapm; R=H (papm), o-Me (o-tapm), m-Me (m-tapm), p-Me (p-tapm), p-Cl (p-Clpapm)) with (NH4)(2)[OsCl6] in 2-methoxyethanol gives two isomers of composition OsCl2(aapm)(2). They are structurally characterised by H-1 NMR spectra and established as the cis-trans-cis (ctc) and cis-cis-cis (ccc) isomer. With reference to the coordination pairs of Cl; N(pyrimidine) (N) and N(azo) (N'), the structure of ctc-OsCl2(p-tapm)(2) is confirmed by an X-ray diffraction study. The complexes exhibit multiple MLCT transitions in the visible to near-IR region. Redox studies show an Os(III)/Os(II) couple at 1.2-1.3 V and Os(IV)/Os(III) couple at similar to2 V versus SCE. EHMO calculations and comparison with analogous ruthenium(II) complexes explain the spectral and redox properties of the complexes. (C) 2002 Published by Elsevier Science Ltd.

Original languageEnglish
Pages (from-to)753-762
Number of pages10
JournalPolyhedron
Volume21
Publication statusPublished - 1 Apr 2002

Keywords

  • arylazopyrimidines
  • osmium(II) complexes
  • geometrical isomers
  • X-ray structures
  • MLCT transitions
  • redox property
  • RAY CRYSTAL-STRUCTURES
  • SPECTRAL CHARACTERIZATION
  • REDOX PROPERTIES
  • BIS<2-(ARYLAZO)PYRIMIDINE> COMPLEXES
  • RUTHENIUM(II) COMPLEXES
  • AROMATIC HYDROXYLATION
  • HOMOGENEOUS CATALYSIS
  • AZO
  • LIGANDS
  • SILVER(I)

Fingerprint

Dive into the research topics of 'Osmium¯azopyrimidine chemistry. Part VII: synthesis, structural characterisation and electrochemistry'. Together they form a unique fingerprint.

Cite this