Photofragment spectroscopy of pi complexes: Au+(C2H4) and Pt+(C2H4)

STRINGER K., Citir M., METZ R.

JOURNAL OF PHYSICAL CHEMISTRY A, vol.108, no.34, pp.6996-7002, 2004 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 108 Issue: 34
  • Publication Date: 2004
  • Doi Number: 10.1021/jp0403691
  • Journal Name: JOURNAL OF PHYSICAL CHEMISTRY A
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.6996-7002
  • Abdullah Gül University Affiliated: No

Abstract

Photodissociation spectra of the classic π complexes Au+(C2H4) and Pt+(C2H4) in the gas phase are reported, providing upper limits to metal−ligand bond strengths of 28 800 cm-1 (344 kJ mol-1) and 19 200 cm-1 (230 kJ mol-1), respectively. The spectrum of Au+(C2H4) features an extended progression in the metal−ligand stretch with a frequency of 176 cm-1, which drops to 160 cm-1 in Au+(C2D4). Hybrid density functional theory (DFT) calculations at the B3LYP level indicate that both complexes adopt a metallocyclopropane structure. The effect of basis set size and flexibility on the metal−ligand dissociation energy is explored. In addition, excited electronic states of both complexes have been investigated by using TD-DFT calculations.

Photodissociation spectra of the classic pi complexes Au+(C2H4) and Pt+(C2H4) in the gas phase are reported, providing upper limits to metal-ligand bond strengths of 28 800 cm(-1) (344 kJ mol(-1)) and 19 200 cm(-1) (230 kJ mol(-1)), respectively. The spectrum of Au'(C2H4) features an extended progression in the metal-ligand stretch with a frequency of 176 cm(-1), which drops to 160 cm-1 in Au+(C2D4). Hybrid density functional theory (DFT) calculations at the B3LYP level indicate that both complexes adopt a metallocyclopropane structure. The effect of basis set size and flexibility on the metal-ligand dissociation energy is explored. In addition, excited electronic states of both complexes have been investigated by using TD-DFT calculations.