TY - JOUR
T1 - The synthesis of highly active iridium(I) complexes and their application in catalytic hydrogen isotope exchange
AU - Brown, Jack A.
AU - Cochrane, Alison Ruth
AU - Irvine, Stephanie
AU - Kerr, William J.
AU - Mondal, Bhaskar
AU - Parkinson, John A.
AU - Paterson, Laura
AU - Reid, Marc
AU - Tuttle, Tell
AU - Andersson, Shalini
AU - Nilsson, Göran N.
N1 - This is the accepted version of the following article: The synthesis of highly active iridium(I) complexes and their application in catalytic hydrogen isotope exchange, Brown, J. A., Cochrane, A. R., Irvine, S., Kerr, W., Mondal, B., Parkinson, J. A., Paterson, L., Reid, M., Tuttle, T., Andersson, S. & Nilsson, G. N. 2014 In : Advanced Synthesis and Catalysis., which has been published in final form at: http://onlinelibrary.wiley.com/doi/10.1002/adsc.201400730/
PY - 2014/11/24
Y1 - 2014/11/24
N2 - A series of robust iridium(I) complexes bearing a sterically encumbered N-heterocyclic carbene ligand, alongside a phosphine ligand, has been synthesised and investigated in hydrogen isotope exchange processes. These complexes have allowed isotope incorporation over a range of substrates with the use of practically convenient deuterium and tritium gas. Moreover, these active catalysts are capable of isotope incorporation to particularly high levels, whilst employing low catalyst loadings and in short reaction times. In addition to this, these new catalyst species have shown flexible levels of chemoselectivity, which can be altered by simple manipulation of preparative approaches. Furthermore, a number of industrially-relevant drug molecules have also been labelled, including the sulfonamide containing drug, Celecoxib. Alongside detailed NMR experiments, initial mechanistic investigations have also been performed, providing insight into both substrate binding energies, and, more importantly, relative energies of key steps in the mechanistic cycle as part of the overall exchange process.
AB - A series of robust iridium(I) complexes bearing a sterically encumbered N-heterocyclic carbene ligand, alongside a phosphine ligand, has been synthesised and investigated in hydrogen isotope exchange processes. These complexes have allowed isotope incorporation over a range of substrates with the use of practically convenient deuterium and tritium gas. Moreover, these active catalysts are capable of isotope incorporation to particularly high levels, whilst employing low catalyst loadings and in short reaction times. In addition to this, these new catalyst species have shown flexible levels of chemoselectivity, which can be altered by simple manipulation of preparative approaches. Furthermore, a number of industrially-relevant drug molecules have also been labelled, including the sulfonamide containing drug, Celecoxib. Alongside detailed NMR experiments, initial mechanistic investigations have also been performed, providing insight into both substrate binding energies, and, more importantly, relative energies of key steps in the mechanistic cycle as part of the overall exchange process.
KW - hydrogen isotope exchange
KW - iridium
KW - catalysis
KW - deuterium
KW - tritium
UR - http://strathprints.strath.ac.uk/50517/
UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1615-4169
U2 - 10.1002/adsc.201400730
DO - 10.1002/adsc.201400730
M3 - Article
SN - 1615-4150
VL - 356
SP - 3551
EP - 3562
JO - Advanced Synthesis and Catalysis
JF - Advanced Synthesis and Catalysis
IS - 17
ER -