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

doi:10.1002/ejic.201701413

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

The synthesis of cationic mono oxo Mo^IV PNP pincer complexes of the type [Mo(PNP^Me-iPr)(O)X]⁺ (X = I, Br) from [Mo(PNP^Me-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(PNP^Me-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(PNP^Me-iPr)(O)I]SbF₆ is presented.

Original language	English
Pages (from-to)	876-884
Number of pages	9
Journal	European Journal of Inorganic Chemistry
Volume	2018
Issue number	7
Early online date	7 Jan 2018
DOIs	https://doi.org/10.1002/ejic.201701413
Publication status	Published - 21 Feb 2018

Keywords

Ligand effects
Molybdenum
Oxo complexes
Phosphines
Pincer ligands

ASJC Scopus subject areas

Inorganic Chemistry

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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 journal › Article › peer-review

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.

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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",

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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

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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

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JO - European Journal of Inorganic Chemistry

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