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Probing the Donor Properties of Pincer Ligands Using Rhodium Carbonyl Fragments: An Experimental and Computational Case Study.

Gemma L ParkerSamantha LauBaptiste LeforestierAdrian B Chaplin
Published in: European journal of inorganic chemistry (2019)
Metal carbonyls are commonly employed probes for quantifying the donor properties of monodentate ligands. With a view to extending this methodology to mer-tridentate "pincer" ligands, the spectroscopic properties [ν(CO), δ 13C, 1 J RhC] of rhodium(I) and rhodium(III) carbonyl complexes of the form [Rh(pincer)(CO)][BArF 4] and [Rh(pincer)Cl2(CO)][BArF 4] have been critically analysed for four pyridyl-based pincer ligands, with two flanking oxazoline (NNN), phosphine (PNP), or N-heterocyclic carbene (CNC) donors. Our investigations indicate that the carbonyl bands of the rhodium(I) complexes are the most diagnostic, with frequencies discernibly decreasing in the order NNN > PNP > CNC. To gain deeper insight, a DFT-based energy decomposition analysis was performed and identified important bonding differences associated with the conformation of the pincer backbone, which clouds straightforward interpretation of the experimental IR data. A correlation between the difference in carbonyl stretching frequencies Δν(CO) and calculated thermodynamics of the RhI/RhIII redox pairs was identified and could prove to be a useful mechanistic tool.
Keyphrases
  • molecular docking
  • single molecule
  • small molecule
  • molecular dynamics
  • data analysis