Abstract
(Diene)rhodium(I) and -iridium(I) derivatives of the pyridinophane ligand L-4 and the analogous macrocycle L-6 have been prepared and characterized [diene = cyclooctadiene (COD) or norbornadiene (NBD)]. In all of the complexes, the ligand is coordinated in a x(3)-(amine)(pyridine)(2) fashion; a dynamic process, believed to be concerted, exchanges free and coordinated amine groups. [(LIr)-Ir-4(COD)](+) can be protonated at the amine nitrogen atom. It reacts with H2O2, but only in the presence of acid, to give an oxocyclooctenyl complex, formally a 4-e(-) oxidation product. X-ray structures of [(LRh)-Rh-4(COD)]PF6, [(LRh)-Rh-6(COD)]PF6, [(LRh)-Rh-6(NBD)]PF6, [((LH)-H-4)Ir(COD)](BF4)(2), and [(LIr)-Ir-4(C8H11O)](PF6)(2) are presented.
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