Results
Title

First Stabilization of 14-Electron Rhodium(I) Complexes by Hemichelation.

Authors

Werlé, Christophe; Bailly, Corinne; Karmazin ‐ Brelot, Lydia; Le Goff, Xavier ‐ Frédéric; Pfeffer, Michel; Djukic, Jean ‐ Pierre

Abstract

Hemichelation is emerging as a new mode of coordination where non-covalent interactions crucially contribute to the cohesion of electron-unsaturated organometallic complexes. This study discloses an unprecedented demonstration of this concept to a Group 9 metal, that is, RhI. The syntheses of new 14-electron RhI complexes were achieved by choosing the anti-[(η6:η6-fluorenyl){Cr(CO)3}2] anion as the ambiphilic hemichelating ligand, which was treated with [{Rh(nbd)Cl}2] (nbd=norbornadiene) and [{Rh(CO)2Cl}2]. The new T-shaped RhI hemichelates were characterized by analytical and structural methods. Investigations using the methods of the DFT and electron-density topology analysis (NCI region analysis, QTAIM theory) confirmed the closed-shell, non-covalent and attractive characters of the interaction between the RhI center and the proximal Cr(CO)3 moiety. This study shows that, by appropriate tuning of the electronic properties of the ambiphilic ligand, truly coordination-unsaturated RhI complexes can be synthesized in a manageable form.

Subjects

ORGANOMETALLIC chemistry; RHODIUM; CHROMIUM; COORDINATION compounds; ELECTRON density; CHELATION

Publication

Angewandte Chemie, 2014, Vol 126, Issue 37, p9985

ISSN

0044-8249

Publication type

Academic Journal

DOI

10.1002/ange.201405240