A Diolefin Diamide Rhodium(I) Complex and Its One-Electron Oxidation Resulting in a Two-Center, Three-Electron Rh–N Bond



A tetracoordinated diolefin diamide rhodium(I) complex 6 with the two amido and olefin groups in mutual trans-position and a butterfly structure has been prepared. This anionic complex undergoes a reversible one-electron oxidation at a remarkably negative potential (E1/2 = –1.22 V vs. Fc/Fc+) to give a stable, paramagnetic, tetracoordinated, planar RhI complex 7. This complex was fully characterized, and all data indicate that this species is best described with an unprecedented two-center, three-electron Rh–N bond. DFT computations were performed to further elucidate the electronic structure, and the results fully agree with the two-center, three-electron Rh–N bond description.