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.
| Original language | English |
|---|---|
| Pages (from-to) | 876-884 |
| Number of pages | 9 |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 2018 |
| Issue number | 7 |
| Early online date | 7 Jan 2018 |
| DOIs | |
| Publication status | Published - 21 Feb 2018 |
Keywords
- Ligand effects
- Molybdenum
- Oxo complexes
- Phosphines
- Pincer ligands
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
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.
In: European Journal of Inorganic Chemistry, Vol. 2018, No. 7, 21.02.2018, p. 876-884.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes
T2 - Interplay between Water and Molecular Oxygen
AU - de Aguiar, Sara R.M.M.
AU - Öztopcu, Özgür
AU - Troiani, Anna
AU - de Petris, Giulia
AU - Weil, Matthias
AU - Stöger, Berthold
AU - Pittenauer, Ernst
AU - Allmaier, Günter
AU - Veiros, Luis F.
AU - Kirchner, Karl
PY - 2018/2/21
Y1 - 2018/2/21
N2 - 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.
AB - 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.
KW - Ligand effects
KW - Molybdenum
KW - Oxo complexes
KW - Phosphines
KW - Pincer ligands
UR - http://www.scopus.com/inward/record.url?scp=85041838510&partnerID=8YFLogxK
U2 - 10.1002/ejic.201701413
DO - 10.1002/ejic.201701413
M3 - Article
VL - 2018
SP - 876
EP - 884
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 7
ER -