Half-sandwich rhodium and iridium metallamacrocycles constructed via C-H activation

Half-sandwich rhodium and iridium complexes with carboxylic acid ligands were combined with pyrazine, 4,4'-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)-ethylene (bpe) to give a series of tetranuclear macrocycles. The metallamacrocycles [(Cp*Rh)4()2(pyrazine)2][OTf]2 (), [(Cp*Rh)4()2(bpy)2][OTf]2 (), [(Cp*Rh)4()2(bpe)2][OTf]4 () and [(Cp*Ir)4()2 (pyrazine)2] () ( = 3-(2-pyridyl)acrylic acid, = 1,4-di(4-carboxyphenyl)benzene) were characterized by elemental analysis, NMR, IR and single-crystal X-ray analyses. Due to the different structures of the carboxylate ligands, the complexes , and were synthesized through double-site C-H activation, and complexes were obtained by one-site C-H activation.