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Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
Author(s) -
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
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701413
Subject(s) - chemistry , pincer movement , cationic polymerization , molybdenum , oxygen , molecular oxygen , medicinal chemistry , oxygen atom , crystallography , stereochemistry , molecule , polymer chemistry , inorganic chemistry , catalysis , organic chemistry
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)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 ‐ i Pr)(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 ‐ i Pr)(O)I]SbF 6 is presented.
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