Speciation and decomposition pathways of ruthenium catalysts used for selective C–H hydroxylation
- Authors
- Type
- Published Article
- Journal
- Advances in Chemical Engineering and Science
- Publisher
- "Scientific Research Publishing, Inc."
- Publication Date
- Jan 14, 2014
- Volume
- 5
- Issue
- 8
- Pages
- 3309–3314
- Identifiers
- DOI: 10.1039/C4SC01050G
- Source
- CCHF
- License
- White
Abstract
Mechanistic insight into a C–H hydroxylation reaction catalysed by [(Me3tacn)RuCl3] has been obtained using desorption electrospray ionization mass spectrometry (DESI-MS) to identify reactive intermediates and to determine the fate of the starting metal complex. Our studies provide direct evidence for the formation of a high-valent dioxo-Ru(VI) species, which is believed to be the active oxidant. Other unexpected Ru-oxo intermediates, however, have been identified and may also function as competent hydroxylating agents. Mass spectral data that substantiate putative mechanisms for catalyst arrest and highlight reactivity differences between [(Me3tacn)RuCl3] and the corresponding tribromide adduct are also described.
