Abstract
Abstract Aryloxide rhodium(I) complexes Rh(OAr)(PPh3)3 (1a: Ar=C6Cl5, 1b: Ar=C6F5, 1c: Ar=C6H4–NO2-4) react with CO in toluene solutions to produce Vaska-type complexes trans-Rh(OAr)(CO)(PPh3)2 (2a: Ar=C6Cl5, 2b: Ar=C6F5, 2c: Ar=C6H4–NO2-4). Carbonylation of a similar complex with PMe3 ligands, Rh(OC6H4–NO2-4)(PMe3)3 (3c), also forms trans-Rh(OC6H4–NO2-4)(CO)(PMe3)2 (4c). Molecular structures of the complexes are determined by X-ray crystallography and NMR spectroscopy. Complex 1a reacts with CO in the absence of solvent to produce a mixture of 2a and complex A, the latter of which shows the IR and 13C{1H} signals due to the carbonyl ligand at different positions from those of 2a. Addition of Et2O to the above mixture turns it into analytically pure 2a. Carbonylation of 1b and 1c under the solvent-free conditions produces complexes B and C as the respective products of the solid–gas reaction. Recrystallization of B and C turns them into 2b and 2c, respectively. Complex 3c also reacts with CO in the solid state to form a mixture of 4c and complex D, although the latter complex is converted slowly into 4c even in the solid state.
Published Version
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