First Stabilization of 14-Electron Rhodium(I) Complexes by Hemichelation†
Christophe Werlé
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorCorinne Bailly
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorDr. Lydia Karmazin-Brelot
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorXavier-Frédéric Le Goff
Département de Chimie, Ecole Polytechnique, Palaiseau cedex (France)
Search for more papers by this authorCorresponding Author
Dr. Michel Pfeffer
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.frSearch for more papers by this authorCorresponding Author
Dr. Jean-Pierre Djukic
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.frSearch for more papers by this authorChristophe Werlé
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorCorinne Bailly
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorDr. Lydia Karmazin-Brelot
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Search for more papers by this authorXavier-Frédéric Le Goff
Département de Chimie, Ecole Polytechnique, Palaiseau cedex (France)
Search for more papers by this authorCorresponding Author
Dr. Michel Pfeffer
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.frSearch for more papers by this authorCorresponding Author
Dr. Jean-Pierre Djukic
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.fr
Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France) http://lcsom.u-strasbg.frSearch for more papers by this authorThis work was supported by the National Research Agency (ANR project WEAKINTERMET-2DA), the Laboratory of Excellence “Chemistry of Complex Systems” and the Centre National de la Recherche Scientifique.
Graphical Abstract
Touching from a distance: The syntheses of unprecedented T-shaped 14-electron RhI hemichelates is made possible by choosing the anti-[(η6:η6-fluorenyl){Cr(CO)3}2]-based benzylic anion as an ambiphilic hemichelating ligand, and treating it with [{Rh(nbd)Cl}2] (nbd=norbornadiene) or [{Rh(CO)2Cl}2].
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.
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