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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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
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author 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
author_facet 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
author_sort de Aguiar, Sara R. M. M.
collection PubMed
description 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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spelling pubmed-64855452019-05-03 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 Eur J Inorg Chem Full Papers 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. John Wiley and Sons Inc. 2018-02-12 2018-02-21 /pmc/articles/PMC6485545/ /pubmed/31057330 http://dx.doi.org/10.1002/ejic.201701413 Text en © 2018 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
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
Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title_full Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title_fullStr Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title_full_unstemmed Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title_short Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
title_sort formation of mono oxo molybdenum(iv) pnp pincer complexes: interplay between water and molecular oxygen
topic Full Papers
url 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
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