Binuclear Aromatic C−H Bond Activation at a Dirhenium Site

The electronically unsaturated dirhenium complex [Re2(CO)8(μ‐H)(μ‐Ph)] (1) has been found to exhibit aromatic C−H activation upon reaction with N,N‐diethylaniline, naphthalene, and even [D6]benzene to yield the compounds [Re2(CO)8(μ‐H)(μ‐η1‐NEt2C6H4)] (2), [Re2(CO)8(μ‐H)(μ‐η2‐1,2‐C10H7)] (3), and [D6]‐1, respectively, in good yields. The mechanism has been elucidated by using DFT computational analyses, and involves a binuclear C−H bond‐activation process. Two Rheniums are better than one: The electronically unsaturated dirhenium complex [Re2(CO)8(μ‐H)(μ‐Ph)] (1) exhibits aromatic C−H activation upon reaction with [D6]benzene to yield [D6]‐1 in good yield. The mechanism has been elucidated by DFT analyses, and involves a binuclear C−H bond‐activation process. N,N‐Diethylaniline and naphthalene also react with 1 to generate [Re2(CO)8(μ‐H)(μ‐η1‐NEt2C6H4)] and [Re2(CO)8(μ‐H)(μ‐η2‐1,2‐C10H7)], respectively.