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 journalArticle

1 Citation (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., ... 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

Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes : Interplay between Water and Molecular Oxygen. / de Aguiar, Sara R.M.M.; Öztopcu, Özgür; Troiani, Anna; de Petris, Giulia; Weil, Matthias; Stöger, Berthold; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F.; Kirchner, Karl.

In: European Journal of Inorganic Chemistry, Vol. 2018, No. 7, 21.02.2018, p. 876-884.

Research output: Contribution to journalArticle

de Aguiar, SRMM, Öztopcu, Ö, Troiani, A, de Petris, G, Weil, M, Stöger, B, Pittenauer, E, Allmaier, G, Veiros, LF & Kirchner, K 2018, 'Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen', European Journal of Inorganic Chemistry, vol. 2018, no. 7, pp. 876-884. https://doi.org/10.1002/ejic.201701413
de Aguiar, Sara R.M.M. ; Öztopcu, Özgür ; Troiani, Anna ; de Petris, Giulia ; Weil, Matthias ; Stöger, Berthold ; Pittenauer, Ernst ; Allmaier, Günter ; Veiros, Luis F. ; Kirchner, Karl. / Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes : Interplay between Water and Molecular Oxygen. In: European Journal of Inorganic Chemistry. 2018 ; Vol. 2018, No. 7. pp. 876-884.
@article{2b57324425344284af5db03e01eff47b,
title = "Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen",
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.",
keywords = "Ligand effects, Molybdenum, Oxo complexes, Phosphines, Pincer ligands",
author = "{de Aguiar}, {Sara R.M.M.} and {\"O}zg{\"u}r {\"O}ztopcu and Anna Troiani and {de Petris}, Giulia and Matthias Weil and Berthold St{\"o}ger and Ernst Pittenauer and G{\"u}nter Allmaier and Veiros, {Luis F.} and Karl Kirchner",
year = "2018",
month = "2",
day = "21",
doi = "10.1002/ejic.201701413",
language = "English",
volume = "2018",
pages = "876--884",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "7",

}

TY - JOUR

T1 - Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes

T2 - Interplay between Water and Molecular Oxygen

AU - de Aguiar, Sara R.M.M.

AU - Öztopcu, Özgür

AU - Troiani, Anna

AU - de Petris, Giulia

AU - Weil, Matthias

AU - Stöger, Berthold

AU - Pittenauer, Ernst

AU - Allmaier, Günter

AU - Veiros, Luis F.

AU - Kirchner, Karl

PY - 2018/2/21

Y1 - 2018/2/21

N2 - 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.

AB - 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.

KW - Ligand effects

KW - Molybdenum

KW - Oxo complexes

KW - Phosphines

KW - Pincer ligands

UR - http://www.scopus.com/inward/record.url?scp=85041838510&partnerID=8YFLogxK

U2 - 10.1002/ejic.201701413

DO - 10.1002/ejic.201701413

M3 - Article

VL - 2018

SP - 876

EP - 884

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 7

ER -