Journal
CHEMICAL SOCIETY REVIEWS
Volume 45, Issue 5, Pages 1197-1210Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cs00566c
Keywords
-
Categories
Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- NRF of Korea through GRL [NRF-2010-00353]
- NRF of Korea through MSIP [2013R1A1A2062737]
- Israel Science Foundation (ISF grant) [1183/13]
Ask authors/readers for more resources
Enzymatic reactions that involve C-H bond activation of alkanes by high-valent iron-oxo species can be explained by the rebound mechanism (RM). Hydroxylation reactions of alkane substrates effected by the reactive compound I (Cpd I) species of cytochrome P450 enzymes are good examples. There was initially little doubt that the rebound paradigm could be carried over in the same form to the arena of synthetic nonheme high-valent iron-oxo or other metal-oxo complexes. However, the active reaction centres of these synthetic systems are not well-caged, in contrast to the active sites of enzymes; therefore, the relative importance of the radical dissociation pathway can become prominent. Indeed, accumulating experimental and theoretical evidence shows that introduction of the non-rebound mechanism (non-RM) is necessary to rationalise the different reactivity patterns observed for synthetic nonheme complexes. In this tutorial review, we discuss several specific examples involving the non-RM while making frequent comparisons to the RM, mainly from the perspective of computational chemistry. We also provide a technical guide to DFT calculations of RM and non-RM and to the interpretations of computational outcomes.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available