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

作者：Rosenthal, Amos J; Vogt, Matthias; de Bruin, Bas^*; Gruetzmacher, Hansjoerg

来源：European Journal of Inorganic Chemistry, 2013, 2013(34): 5831-5835.

DOI：10.1002/ejic.201301207

• Radicals
• Ab initio calculations
• EPR spectroscopy
• Redox chemistry
• Rhodium

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 (E-1/2 = -1.22 V vs. Fc/Fc( )) to give a stable, paramagnetic, tetracoordinated, planar Rh-I 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.

• 出版日期2013-12-2
• 单位中山大学