By ed. by Martin Hiersemann
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Extra info for Activating Unreactive Substrates The Role of Secondary Interactions
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.
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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 .
Activating Unreactive Substrates The Role of Secondary Interactions by ed. by Martin Hiersemann