title: d8 rhodium and iridium complexes of corannulene.
abstract: [(COE)2M]+ fragments (M = Rh, Ir; COE = cyclooctene) react with corannulene to give eta6-bound complexes [(COE)2Rh(eta6-C20H10)]PF6 and [(COE)2Ir(eta6-C20H10)]PF6. Both compounds were characterized by X-ray diffraction studies, and binding in the solid state is compared with that of their aromatic analogues [(COE)2M(eta6-arene)]PF6 (aryl = benzene and phenanthrene). Solution NMR studies show that the [(COE)2Rh]+ fragment walks over the curved aromatic surface of corannulene, whereas the Ir analogue is not fluxional. Experimental as well as computational studies suggest that inter-ring movement of the Rh complex follows a hub migration mechanism. Initial reactivity studies indicate that the [(COE)2M]+ fragments can undergo chemical transformations, such as transfer dehydrogenation and substitution reactions, while still bound to corannulene.
authors.affiliation: Institute of Organic Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland. jss@oci.unizh.ch
authors.forename: Jay S
authors.initials: JS
authors.lastname: Siegel
authors.forename: Kim K
authors.initials: KK
authors.lastname: Baldridge
authors.forename: Anthony
authors.initials: A
authors.lastname: Linden
authors.forename: Reto
authors.initials: R
authors.lastname: Dorta