A phosphino,oxazoline P,N-bidentate ligand, 4, containing 3,5-di-tert-butylphenyl groups has been prepared. In the Heck arylation of dihydrofuran, 4 is shown to afford higher ee's than either 2 or 3, the unsubstituted and m-dimethylphenyl analogues, respectively. Several Pd(0) complexes of 4 are reported. The exchange dynamics of Pd(4)(dba) are shown to involve an interconversion of diastereomers via an intramolecular process. The X-ray structure for PdCl2(4), 8, was determined by X-ray diffraction methods. Comparison of data with PdCl2(2), 9, and PdCl2(3), 10, suggests that differing amounts of stacking influence the structures of these relatively simple Pd complexes, with 9 and 10 revealing the strongest, pi-pi interactions. An estimation of the van der Waals energies involved in the interaction supports a ca. 4 kcal/mol stabilization via pi-pi stacking.

Dialkyl effect on enantioselectivity: pi-stacking as a structural feature in P,N complexes of palladium(II) / Dotta, P; Magistrato, Alessandra; Rothlisberger, U; Pregosin, Ps; Albinati, A.. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 21:14(2002), pp. 3033-3041. [10.1021/om020314q]

Dialkyl effect on enantioselectivity: pi-stacking as a structural feature in P,N complexes of palladium(II)

MAGISTRATO, ALESSANDRA;
2002-01-01

Abstract

A phosphino,oxazoline P,N-bidentate ligand, 4, containing 3,5-di-tert-butylphenyl groups has been prepared. In the Heck arylation of dihydrofuran, 4 is shown to afford higher ee's than either 2 or 3, the unsubstituted and m-dimethylphenyl analogues, respectively. Several Pd(0) complexes of 4 are reported. The exchange dynamics of Pd(4)(dba) are shown to involve an interconversion of diastereomers via an intramolecular process. The X-ray structure for PdCl2(4), 8, was determined by X-ray diffraction methods. Comparison of data with PdCl2(2), 9, and PdCl2(3), 10, suggests that differing amounts of stacking influence the structures of these relatively simple Pd complexes, with 9 and 10 revealing the strongest, pi-pi interactions. An estimation of the van der Waals energies involved in the interaction supports a ca. 4 kcal/mol stabilization via pi-pi stacking.
2002
21
14
3033
3041
Dotta, P; Magistrato, Alessandra; Rothlisberger, U; Pregosin, Ps; Albinati, A.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11767/32687
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