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First Stabilization of 14‐Electron Rhodium(I) Complexes by Hemichelation
Author(s) -
Werlé Christophe,
Bailly Corinne,
KarmazinBrelot Lydia,
Le Goff XavierFrédéric,
Pfeffer Michel,
Djukic JeanPierre
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201405240
Subject(s) - rhodium , norbornadiene , chemistry , covalent bond , moiety , ligand (biochemistry) , metal , stereochemistry , crystallography , computational chemistry , organic chemistry , catalysis , receptor , biochemistry
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, Rh I . The syntheses of new 14‐electron Rh I complexes were achieved by choosing the anti‐ [(η 6 :η 6 ‐fluorenyl){Cr(CO) 3 } 2 ] anion as the ambiphilic hemichelating ligand, which was treated with [{Rh(nbd)Cl} 2 ] (nbd=norbornadiene) and [{Rh(CO) 2 Cl} 2 ]. The new T‐shaped Rh I 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 Rh I 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 Rh I complexes can be synthesized in a manageable form.