A Diolefin Diamide Rhodium(I) Complex and Its One‐Electron Oxidation Resulting in a Two‐Center, Three‐Electron Rh–N Bond. Issue 34 (29th October 2013)

• Record Type: Journal Article
• Authors: Rosenthal, Amos J.; Vogt, Matthias; de Bruin, Bas; Grützmacher, Hansjörg
• Is Part Of: European journal of inorganic chemistry. Issue 34(2013)
• Page Start: 5831
• Page End: 5835
• Publication Date: 2013-10-29
• Subjects: Radicals -- Ab initio calculations -- EPR spectroscopy -- Redox chemistry -- Rhodium; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301207
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: A tetracoordinated diolefin diamide rhodium(I) complex6 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 complex7 . 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. Abstract : Anionic Rh I complex1 with two amido groups in the trans ‐position is remarkably stable. This complex is easily oxidized by one electron to give a stable, paramagnetic, tetracoordinated planar Rh complex, which was fully characterized. The equally distributed spin density over the Rh–N bond, bolstered by DFT computations, indicates an unprecedented two‐center, three‐electron Rh–N bond.