By ed. by Martin Hiersemann
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Additional resources for Activating Unreactive Substrates The Role of Secondary Interactions
4). 4 Intramolecular hydrogen bond interactions between coordinated substrate X and guanidines. In order to screen our chemistry for the existence of a secondary ligand effect, we are looking for differences in the reactivity patterns of N-peralkylated and NHfunctionalized guanidine ligand complexes. 5 The Chemistry of Guanidine Copper Complexes Peralkylguanidines are strong sp2 nitrogen donors that typically display shorter dative bonds to a metal cation than corresponding tertiary amines as sp3 donor ligands.
The question arose whether our structural model might serve as a biomimetic functional model as well. With this in mind the group of Karlin investigated the reactions of [(TMG3tren)Cu(h1-O2)]þ with substituted phenols. There was an ongoing debate about whether the superoxo or perhaps other oxygen species might be the most potent oxidants in this system. A most relevant insight of this study is that a hydroperoxo complex that is formed via hydrogen abstraction of the precatalytic (resting) superoxo species at a phenol substrate will lead to a more potent oxidizing hydroperoxo species [(TMG3tren)Cu(h1-OOH)]þ .
Giorgi, M. and Reinaud, O. (2001) Journal of the American Chemical Society, 123, 8442–8443. , Goetz, S. and McKee, V. (2002) Angewandte Chemie – International Edition, 41, 4553–4556. J. J. (2000) Coordination Chemistry Reviews, 200–202, 443–485. 38 Kersting, B. (2004) Zeitschrift fur Anorganische und Allgemeine Chemie, 630, 765–780. , Fritz, T. and Hausmann, J. (1999) European Journal of Inorganic Chemistry, 2167–2172. H. and Kersting, B. (2001) Zeitschrift fur Naturforschung, 56b, 437–439. , Steinfeld, G.
Activating Unreactive Substrates The Role of Secondary Interactions by ed. by Martin Hiersemann