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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
d8 rhodium and iridium complexes of corannulene
Jay S Siegel1, Kim K Baldridge, Anthony Linden
1Institute of Organic Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland. jss@oci.unizh.ch
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.
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Structure of Conjugated Dienes
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...

