Synthesis and Characterization of Phosphorus-Containing Isocyclam Macrocycles and Their Nickel Complexes.

The tetradentate azamacrocycle cyclam (=1,4,8,11-tetraazacyclotetradecane) was studied profoundly for the coordination of transition metal ions, and the resulting complexes were investigated extensively for their catalytic performance in, e.g., O 2 activation and electrocatalytic CO 2 reduction. Although the successful synthesis of analogous P 4 macrocycles was described earlier, no tetradentate N,P mixed 14-membered macrocycles have been prepared to date and their chemistry remains elusive. Thus, in this work, we showcase the synthesis of phospha-aza mixed cyclam-based macrocycles by selectively "exchanging" one or two secondary amines in the macrocycle isocyclam (=1,4,7,11-tetraazacyclotetradecane) with tertiary phosphines. In addition, we herein present the preparation of the corresponding nickel complexes along with their complex chemical and structural characterization to provide first coordination studies.