By ed. by Martin Hiersemann

ISBN-10: 352730715X

ISBN-13: 9783527307159

ISBN-10: 3527308253

ISBN-13: 9783527308255

ISBN-10: 3527310746

ISBN-13: 9783527310746

ISBN-10: 3527311319

ISBN-13: 9783527311316

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Extra info for Activating Unreactive Substrates The Role of Secondary Interactions

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Crystallization using many different ligand–anion– solvent combinations ultimately gave non-disordered single crystals suitable for an XRD analysis. 9. 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.

2005) Journal of the American Chemical Society, 127, 15738. 14 Raab, V. and Sundermeyer, J. DE 101 43566. , Steinmann, M. and Henkel, G. (1998) Zeitschrift fur Naturforschung, 53 b, 997. 16 (a) Schwesinger, R. and Schlemper, H. G. (1993) Angewandte Chemie (International Edition in English), 32, 1361. , Huang, X. L. (2002) Journal of the American Chemical Society, 124, 7421. D. W. (2006) Science, 314, 1124. , Grimme, S. W. (2007) Chemical Communications, 5072. , Schorm, A. and Sundermeyer, J. (2000) Zeitschrift Fur Anorganische Und Allgemeine Chemie, 626, 1583.

In this respect it is interesting to compare the basicity of the chelating naphthalene-based pincer ligands with the basicity of the monodentate phenyl-substituted proton acceptors cut in half. The secondary chelate effect increases basicity of guanidines by about 4 orders and of phosphazenes by nearly 9 orders of magnitude! Because of the secondary intramolecular interaction, HMPN becomes about two orders of magnitude more basic than monodentate Schwesinger base tert-Bu-P1. 3 Some Perspectives in Proton Sponge Chemistry TMGN, despite its narrow bite angle, can be used as a constrained chelate ligand to metal cations such as Be2þ and even to larger coinage and platinum metals [12].

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Activating Unreactive Substrates The Role of Secondary Interactions by ed. by Martin Hiersemann


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