Formation of mono oxo molybdenum(IV) PNP pincer complexes: interplay between water and molecular oxygen
01 Pubblicazione su rivista
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
ISSN: 1434-1948
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.