Formation of Mono Oxo Molybdenum(IV) PNP Pincer Complexes: Interplay between Water and Molecular Oxygen.

ABSTRACT: 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)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-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(PNP^Me-iPr)(O)I]SbF₆ is presented.

SUBMITTER: de Aguiar SRMM 

PROVIDER: S-EPMC6485545 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature