Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen

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)X(2)] is described. These compounds are coordinatively unsaturated and feature a strong Mo≡O triple bond. The formation of these complexes proceeds via cationic 14...

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Detalles Bibliográficos
Autores principales: 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
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
Materias:
Full Papers
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6485545/
https://www.ncbi.nlm.nih.gov/pubmed/31057330
http://dx.doi.org/10.1002/ejic.201701413
Descripción
Sumario: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)X(2)] 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 (18)O labeled water (H(2) (18)O) and molecular oxygen ((18)O(2)) 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]SbF(6) is presented.

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