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

Research output: Contribution to journalArticlepeer-review

8 Citations (SciVal)

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

Funding

Financial support by the Austrian Science Fund (FWF) (Project No. P29584-N28), by Fundação para a Ciência e Tecnologia, FCT (PEst-OE/QUI/UI0100/2013) and by Sapienza University of Rome is gratefully acknowledged. The X-ray center of the Vienna University of Technology is acknowledged for financial support and for providing access to the single-crystal diffractometer.

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

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