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Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen
European Journal of Inorganic Chemistry ( IF 2.3 ) Pub Date : 2018-02-12 , DOI: 10.1002/ejic.201701413
Sara R. M. M. de Aguiar 1 , Özgür Öztopcu 1 , Anna Troiani 2 , Giulia de Petris 2 , Matthias Weil 3 , Berthold Stöger 4 , Ernst Pittenauer 3 , Günter Allmaier 3 , Luis F. Veiros 5 , Karl Kirchner 1
Affiliation  

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.

中文翻译:

Mono Oxo Molybdenum (IV) PNP 钳形配合物的形成:水和分子氧之间的相互作用

描述了从 [Mo(PNPMe-iPr)(CO)X2] 合成 [Mo(PNPMe-iPr)(O)X]+ (X = I, Br) 类型的阳离子单氧代 MoIV PNP 钳形配合物。这些化合物是配位不饱和的,具有很强的 Mo≡O 三键。这些配合物的形成通过阳离子 14e 中间体 [Mo(PNPMe-iPr)(CO)X]+ 进行,并且需要分子氧和水。使用 18O 标记水 (H2·18O) 和分子氧 (18O2) 进行的 ESI MS 测量表明,水在 Mo≡O 键的形成中起着至关重要的作用。提供了一种基于 DFT 计算的合理机制。展示了 [Mo(PNPMe-iPr)(O)I]SbF6 的 X 射线结构。
更新日期:2018-02-12
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