Multiple C−H Bond Activations in Corannulene by a Dirhenium Complex

The reaction of Re 2 (CO) 8 (μ‐C 6 H 5 )(μ‐H), 1 with corannulene (C 20 H 10 ) yielded the product Re 2 (CO) 8 (μ‐H)(μ‐η 2 ‐1,2‐C 20 H 9 ), 2 (65 % yield) containing a Re 2 metalated corannulene ligand formed by loss of benzene from 1 and the activation of one of the CH bonds of the nonplanar corannulene molecule by an oxidative‐addition to 1 . The corannulenyl ligand has adopted a bridging η 2 ‐σ+π coordination to the Re 2 (CO) 8 grouping. Compound 2 reacts with a second equivalent of 1 to yield three isomeric doubly metalated corannulene products: Re 2 (CO) 8 (μ‐H)(μ‐η 2 ‐1,2‐μ‐η 2 ‐10,11‐C 20 H 8 )Re 2 (CO) 8 (μ‐H), 3 (35 % yield), Re 2 (CO) 8 (μ‐H)(μ‐η 2 ‐2,1‐μ‐η 2 ‐10,11‐C 20 H 8 )Re 2 (CO) 8 (μ‐H), 4 (12 % yield), and Re 2 (CO) 8 (μ‐H)(μ‐η 2 ‐1,2‐μ‐η 2 ‐11,10‐C 20 H 8 )Re 2 (CO) 8 (μ‐H), 5 (12 % yield), by a second CH activation on a second rim double bond on the corannulene molecule. The isomers differ by the relative orientations of the coordinated Re 2 (CO) 8 (μ‐H) groupings. All new products were characterized structurally by single crystal X‐ray diffraction analysis.