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Additional info for Activating Unreactive Substrates The Role of Secondary Interactions
This investigation was funded by the DFG priority program 1118 focussing on the activation of unreactive substrates via secondary ligand substrate interactions. The present account discusses a selection of our results in the context of the work of other groups. 1 Properties of the Guanidine Functionality The most prominent feature of a guanidine base is its pronounced proton acceptor character. Peralkyl guanidines, in particular, are among the strongest purely organic neutral bases known. 00. 62 .
Grimme, S. W. (2007) Chemical Communications, 5072. , Schorm, A. and Sundermeyer, J. (2000) Zeitschrift Fur Anorganische Und Allgemeine Chemie, 626, 1583. , Plackmeyer, J. and Sundermeyer, J. (2001) European Journal of Inorganic Chemistry, 1937. , Saak, W. and Henkel, G. (2000) Journal of The Chemical Society-Dalton Transactions, 3473. , Kipke, J. and Sundermeyer, J. (2001) Inorganic Chemistry, 40, 6964. , Merz, M. and Sundermeyer, J. (2001) Journal of Molecular Catalysis AChemical, 175, 51. , Sundermeyer, J.
8 Formation and degradation pathways of a proposed mononuclear oxo species [(DMEG3tren)Cu(O)]þ . Molecular structure of [(DMEG3trenO)Cu]ClO4ÁH2O. It is plausible that the oxidants, solvated PhIO(MeCN)n or TsN3, are activated via electron transfer from Cu(I). This might proceed either via an inner-sphere mechanism and a Cu(I) precoordinated oxidant or via an outer-sphere mechanism. The result of a single-electron transfer would be the formation of oxidant radical anions coordinated to Cu(II) and elimination of stable leaving groups N2 or PhI.