(Diene)rhodium and -iridium Complexes of Pyridinophane Ligands

• Published in: European journal of inorganic chemistry Vol. 2002; no. 2; pp. 457 - 464
• Main Authors: Sciarone, Timo, Hoogboom, Johan, Schlebos, Paul P. J., Budzelaar, Peter H. M., de Gelder, René, Smits, Jan M. M., Gal, Anton W.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 01.02.2002; WILEY‐VCH Verlag GmbH
• Subjects: Diene ligands; Fluxionality; Iridium; Oxidations; Rhodium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/1099-0682(20022)2002:2<457::AID-EJIC457>3.0.CO;2-P

(Diene)rhodium(I) and ‐iridium(I) derivatives of the pyridinophane ligand L4 and the analogous macrocycle L6 have been prepared and characterized [diene = cyclooctadiene (COD) or norbornadiene (NBD)]. In all of the complexes, the ligand is coordinated in a κ3‐(amine)(pyridine)2 fashion; a dynamic process, believed to be concerted, exchanges free and coordinated amine groups. [L4Ir(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 [L4Rh(COD)]PF6, [L6Rh(COD)]PF6, [L6Rh(NBD)]PF6, [(L4H)Ir(COD)](BF4)2, and [L4Ir(C8H11O)](PF6)2 are presented.