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Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
Sara R M M de Aguiar1, Özgür Öztopcu1, Anna Troiani2
1Institute of Applied Synthetic Chemistry Vienna University of Technology Getreidemarkt 9 1060 Vienna Austria.
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.
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