Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen. Issue 7 (12th February 2018)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: European journal of inorganic chemistry. Issue 7(2018)
• Page Start: 876
• Page End: 884
• Publication Date: 2018-02-12
• Subjects: Molybdenum -- Pincer ligands -- Phosphines -- Oxo complexes -- Ligand effects; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701413
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The synthesis of cationic mono oxo Mo IV PNP pincer complexes of the type [Mo(PNP Me ‐ i Pr)(O)X] + (X = I, Br) from [Mo(PNP Me ‐ i Pr)(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 ‐ i Pr)(CO)X] + and requires both molecular oxygen and water. ESI MS measurements with 18 O labeled water (H2 18 O) and molecular oxygen ( 18 O2 ) 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 ‐ i Pr)(O)I]SbF6 is presented. Abstract : The synthesis of cationic mono oxo Mo IV PNP pincer complexes of the type [Mo(PNP Me ‐ i Pr)(O)X] + (X = I, Br) is described. These compounds are coordinatively unsaturated and feature a strong Mo≡O triple bond. Their formation requires cooperation between molecular oxygen and water.