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Solvent‐Dependent Interconversions between Rh I , Rh II , and Rh III Complexes of an Aryl–Monophosphine Ligand
Author(s) -
Montag Michael,
Leitus Gregory,
Shimon Linda J. W.,
BenDavid Yehoshoa,
Milstein David
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700805
Subject(s) - chemistry , rhodium , solvent , acetonitrile , aryl , acetone , dichloromethane , ligand (biochemistry) , medicinal chemistry , alkyl , reagent , cyclooctene , hydride , redox , solvent effects , inorganic chemistry , organic chemistry , catalysis , hydrogen , biochemistry , receptor
Reaction of the aryl‐monophosphine ligand α 2 ‐(diisopropylphosphino)isodurene ( 1 ) with the Rh I precursor [Rh(coe) 2 (acetone) 2 ]BF 4 (coe=cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent‐stabilized Rh III alkyl‐hydride complex ( 2 ) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear η 6 ‐arene Rh II complex ( 5 ) was obtained in the absence of added redox reagents. Moreover, when acetonitrile was added to a solution of either the Rh II or Rh III complexes, a new solvent‐stabilized, noncyclometalated Rh I complex ( 6 ) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.