RHODIUM(I) COMPLEXES OF A CHIRAL AMIDOPHOSPHINE-PHOSPHINITE CHELATE -DINUCLEAR COMPLEXES WITH CHELATING AND BRIDGING LIGANDS

Rh(I) complexes of the chiral bidentate ligand no-2-diphenylphosphinox y-3,3,N-trimethylbutyramide (1) are reported. Two equivalents of 1 rea ct with [RhCl(1,5-COD)](2) slowly in MeOH to afford an isolable unsymm etrical dinuclear complex [(1)Rh(mu-Cl)(mu-1)Rh(1,5-COD)]Cl (2), and t he symmetrical dinuclear compound [Rh(mu-Cl)(1)](2), which exists in t wo forms, sym-trans (3) and sym-cis (4), in solution. In CD2Cl2 soluti on, 2 converts slowly to 3 and 4. Two-dimensional exchange spectroscop y on 2 reveals an intramolecular and an intermolecular process during the reaction in CD2Cl2. A second dinuclear cation, [(1)Rh(mu-Cl)(mu-1) Rh(1)](+) (6), containing 3 equiv of 1, can be prepared from the PF6 a nalogue of 2. [Rh(1,5-COD)(1)]OTf (7a), [RhCl(PPh3)(1)] (8), [Rh(CO)(P Ph3)(1)]Cl (9), air-sensitive [Rh(1)(solvent)(2)]OTf (10), and [RhCl(C NBut)(1)] (11) are reported. The solid-state structures for 3 and 7a h ave been determined by X-ray diffraction.