Speciation and decomposition pathways of ruthenium catalysts used for selective C-H hydroxylation

Mechanistic insight into a C-H hydroxylation reaction catalysed by [(Me 3 tacn)RuCl 3 ] 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 eviden...

Full description

Saved in:
Bibliographic Details
Published in:Chemical science (Cambridge) 2014-01, Vol.5 (8), p.339-3314
Main Authors: Flender, Cornelia, Adams, Ashley M, Roizen, Jennifer L, McNeill, Eric, Du Bois, J, Zare, Richard N
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Hydroxylation
Ionization
Mass spectrometry
Ruthenium
Speciation
Spectra
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Mechanistic insight into a C-H hydroxylation reaction catalysed by [(Me 3 tacn)RuCl 3 ] 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 [(Me 3 tacn)RuCl 3 ] and the corresponding tribromide adduct are also described. Mechanistic insight into the C-H hydroxylation reaction catalysed by [(Me 3 tacn)RuCl 3 ] 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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c4sc01050g