By ed. by Martin Hiersemann
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Extra info for Activating Unreactive Substrates The Role of Secondary Interactions
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. Because of their donor capability and perfect charge delocalization they stabilize cationic and dicationic complexes and in some cases even copper(III) complexes or complex intermediates. On the other hand guanidines have a softer character compared to amine ligands. In this respect, it is a great advantage that copper(I) guanidine complexes do not tend to disproportionate into copper and copper(II).
Furthermore, we were not able to transfer the green crystals into a SQUID capillary at temperatures below À40 C. However, we were able to employ the Evans method for the measurement of the magnetic susceptibility in acetone at 190 K [30, 31]. 83 mB of a ground-state triplet species. This explains the nmr results, with large paramagnetic shifts, that were obtained. The message is that the spins in this end-on superoxo complex are ferromagnetically coupled, whereas they are antiferromagnetically coupled in all side-on superoxo complexes known so far.
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. ) that are coordinatively activated and partially reduced at the reactive metal site. The activation principle for corresponding zinc complexes would be proton transfer from a coordinatively activated, slightly proton acidic substrate XH to one of the superbasic pendant guanidine arms.