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

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The use of the N-alkylated macrocycles in place of the unmodified analogs influences many properties of the binuclear complexes, including color, molecular and electronic structure, hydrogen bonding interactions, redox potential, complex stability, and ground spin-state. The reactivity is also greatly affected as shown by the activation and transformation of small molecules such as CO2, the highly diastereoselective cis-bromination of a,b-unsaturated carboxylate coligands, and some regioselective Diels–Alder reactions.

At the same time chelating guanidine ligands have been independently developed by the group of G. Henkel [22]. 2. 2 Selected bidentate, tridentate and tetradentate guanidine ligands developed in this research program. Tame ¼ 1,1,1-Tris(aminomethyl)ethane, Tren ¼ tris(2aminoethyl)amine. This research program focussed on the guanidine coordination chemistry of copper and zinc. Two working concepts were followed. It was proposed that superbasic tripodal and sterically demanding tren-derived guanidine ligands when coordinated to copper(I) would create a very electron-rich metal center perfectly embedded in a molecular pocket.

Kersting, B. and Steinfeld, G. (2001) Chemical Communications, 1376–1377. , Steinfeld, G. and Kersting, B. (2005) European Journal of Inorganic Chemistry, 2223–2234. , Gregor, T. and Kersting, B. (2006) Angewandte Chemie – International Edition, 45, 101–104. , Lozan, V. and Kersting, B. (2007) Synthesis, 3706–3712. Gressenbuch, M. D. Thesis, Universit€at Leipzig. Siedle, G. and Kersting, B. (2003) Zeitschrift fur Anorganische und Allgemeine Chemie, 629, 2083–2090. Gressenbuch, M. and Kersting, B.

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