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Multiple C−H Bond Activations in Corannulene by a Dirhenium Complex
Author(s) -
Adams Richard D.,
Dhull Poonam,
Pennachio Matthew,
Petrukhina Marina A.,
Smith Mark D.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806405
Subject(s) - corannulene , chemistry , yield (engineering) , benzene , molecule , ligand (biochemistry) , crystallography , crystal structure , stereochemistry , organic chemistry , materials science , biochemistry , receptor , metallurgy
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.