Filtering the NMR Spectra of Mixtures by Coordination to Paramagnetic Cu 2 .

The paramagnetic spin relaxation (PSR) filter allows the selective NMR signal suppression of components in mixtures according to their complexation ability to a paramagnetic ion. It relies on the faster relaxation of nuclei in paramagnetic environments and thus is complementary to classical diffusion and relaxation filters. So far, the PSR filter has established Gd 3+ as the sole PSR agent, restricting the paramagnetic filtering repertoire. Herein, we present Cu 2+ as a robust PSR agent with characteristic filtering properties. While Gd 3+ depends on unspecific ion-pair interactions with anionic components, Cu 2+ stands out for filtering species via ordered coordination complexes. An evaluation of the paramagnetic effect of Cu 2+ over more than 50 small molecules and polymers has unveiled different sensitivities to Cu 2+ (especially high for pyridines, diamines, polyamines, and amino alcohols) and precise filtering conditions for mixtures ( 1 H, COSY, and HMQC) that were challenged with a test bed of commercial drugs. The advantage of integrating Cu 2+ and Gd 3+ for the stepwise PSR filtering of complex mixtures is also shown.