Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen

Sara R.M.M. de Aguiar, Özgür Öztopcu, Anna Troiani, Giulia de Petris, Matthias Weil, Berthold Stöger, Ernst Pittenauer, Günter Allmaier, Luis F. Veiros, Karl Kirchner

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2 Citations (Scopus)

Abstract

The synthesis of cationic mono oxo MoIV PNP pincer complexes of the type [Mo(PNPMe-iPr)(O)X]+ (X = I, Br) from [Mo(PNPMe-iPr)(CO)X2] is described. These compounds are coordinatively unsaturated and feature a strong Mo≡O triple bond. The formation of these complexes proceeds via cationic 14e intermediates [Mo(PNPMe-iPr)(CO)X]+ and requires both molecular oxygen and water. ESI MS measurements with 18O labeled water (H2 18O) and molecular oxygen (18O2) indicates that water plays a crucial role in the formation of the Mo≡O bond. A plausible mechanism based on DFT calculations is provided. The X-ray structure of [Mo(PNPMe-iPr)(O)I]SbF6 is presented.

Original languageEnglish
Pages (from-to)876-884
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Volume2018
Issue number7
Early online date7 Jan 2018
DOIs
Publication statusPublished - 21 Feb 2018

Keywords

  • Ligand effects
  • Molybdenum
  • Oxo complexes
  • Phosphines
  • Pincer ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

de Aguiar, S. R. M. M., Öztopcu, Ö., Troiani, A., de Petris, G., Weil, M., Stöger, B., Pittenauer, E., Allmaier, G., Veiros, L. F., & Kirchner, K. (2018). Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen. European Journal of Inorganic Chemistry, 2018(7), 876-884. https://doi.org/10.1002/ejic.201701413