A palladium(II) complex containing both carbonyl and imine oxime ligands: Crystal structure, experimental and theoretical UV-vis, IR and NMR studies


Kaya Y., Icsel C., YILMAZ V. T. , Buyukgungor O.

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, vol.108, pp.133-140, 2013 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 108
  • Publication Date: 2013
  • Doi Number: 10.1016/j.saa.2013.01.054
  • Journal Name: SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.133-140
  • Keywords: Imine oxime, Carbonyl oxime, Palladium(II), Crystal structure, DFT calculations, AB-INITIO, CONFORMATIONAL-ANALYSIS, PLATINUM(II) COMPLEXES, MOLECULAR-STRUCTURES, VIBRATIONAL ANALYSIS, INFRARED-SPECTRA, MATRIX-ISOLATION, METAL-COMPLEXES, GAS-PHASE, ACID
  • Karadeniz Technical University Affiliated: No

Abstract

A new palladium(II) complex, [Pd(ppeieo)(inap)]center dot DMSO (ppeieo = (1E,2E)-phenyl-[(1-phenylethyl)imino]-ethanal oxime and imp = isonitrosoacetophenone) has been synthesized and characterized by elemental analysis, UV-vis, IR, NMR. X-ray diffraction analysis of the DMSO solvate of the complex shows that the palladium(II) ion is coordinated in a distorted square-planar geometry by ppeieo and map, which is formed during the hydrolysis of ppeieo. DFT (B3LYP/LANL2DZ) calculations on the complex have been carried out to correlate geometry and spectroscopic properties such as electronic, vibrational and NMR chemical shifts. The complete vibrational frequency assignments were made and the calculation results were applied to simulate infrared spectra of the title compound which shows good agreement with observed spectra. The calculated HOMO and LUMO energies show that several transitions including the pi -> pi* and charge transfer occur within the molecule. The chemical shifts reasonably correspond to the calculated spectra. (c) 2013 Elsevier B.V. All rights reserved.