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 molec-ular oxygen and water. ESI MS measurements with 18O labeled water (H218O) 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.

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. - ISSN 1434-1948. - STAMPA. - 7(2018), pp. 876-884. [10.1002/ejic.201701413]

Formation of mono oxo molybdenum(IV) PNP pincer complexes: interplay between water and molecular oxygen

Anna Troiani
Methodology
;
Giulia de Petris
Investigation
;
2018

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 molec-ular oxygen and water. ESI MS measurements with 18O labeled water (H218O) 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.
molybdenum; pincer ligands; phosphines; oxo complexes; ligand effects
01 Pubblicazione su rivista::01a Articolo in rivista
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. - ISSN 1434-1948. - STAMPA. - 7(2018), pp. 876-884. [10.1002/ejic.201701413]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1081059
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