We have studied the effect of pressure on the configurational inversion reaction at the metal centre of the chiral tris-(cyclic O,O'1(R),2(R)-dimethylethylene dithiophosphato) chromium(III) complexes, Λ(-)589Cr[(R,R)bdtp]3 and Δ(+)589Cr[(R,R)bdtp]3, in solutions of different solvents. We have observed positive or negative Cotton effects, assigned to the 4A2→4T2 transition of the metal ion in the visible region, and their evolution on increasing pressure. At equilibrium and at room conditions one observes a prevalence of the Δ-(R,R)(R,R)(R,R) diastereoisomer in CHCl3 or CH2Cl2 and of the Λ- one in THF. On increasing the pressure a change in the inversion equilibrium occurs, producing an increase in the concentration of the Λ-(R,R)(R,R)(R,R) form in all solvents.

Configurational equilibrium and CD spectra under pressure of chiral octahedral complexes: Λ- and Δ-Cr[(-)(R,R)bdtp]3

BENEDETTI, MICHELE;
1999

Abstract

We have studied the effect of pressure on the configurational inversion reaction at the metal centre of the chiral tris-(cyclic O,O'1(R),2(R)-dimethylethylene dithiophosphato) chromium(III) complexes, Λ(-)589Cr[(R,R)bdtp]3 and Δ(+)589Cr[(R,R)bdtp]3, in solutions of different solvents. We have observed positive or negative Cotton effects, assigned to the 4A2→4T2 transition of the metal ion in the visible region, and their evolution on increasing pressure. At equilibrium and at room conditions one observes a prevalence of the Δ-(R,R)(R,R)(R,R) diastereoisomer in CHCl3 or CH2Cl2 and of the Λ- one in THF. On increasing the pressure a change in the inversion equilibrium occurs, producing an increase in the concentration of the Λ-(R,R)(R,R)(R,R) form in all solvents.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11587/105930
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