ic6b01323_si_001.cif (6.39 MB)
Synthesis of Silver(I) and Gold(I) Complexes Containing Enantiopure Pybox Ligands. First Assays on the Silver(I)-Catalyzed Asymmetric Addition of Alkynes to Imines
dataset
posted on 2016-08-08, 13:48 authored by Gustavo
M. Borrajo-Calleja, Eire de Julián, Esther Bayón, Josefina Díez, Elena Lastra, Isabel Merino, M. Pilar GamasaDinuclear complexes
[Ag2(CF3SO3){(S,S)-iPr-pybox}2][CF3SO3] (1), [Ag2(R-pybox)2][X]2 [R-pybox = 2,6-bis[4-(S)-isopropyloxazolin-2-yl]pyridine
(S,S)-iPr-pybox and X = PF6 (2) and BF4 (3); R-pybox = 2,6-bis[(3aS,8aR)-8,8a-dihydro-3aH-indeno[1,2-d]oxazol-2-yl]pyridine (3aS,3a′S,8aR,8a′R)-indane-pybox
and X = CF3SO3 (4)], [Ag2{(S,S)-iPr-pybox}{(3aS,3a′S,8aR,8a′R)-indane-pybox}][CF3SO3]2 (5), and [Ag2(R-pybox)3][X]2 [R-pybox = (3aS,3a′S,8aR,8a′R)-indane-pybox and X = CF3SO3 (10), SF6 (11), and PF6 (12)] as well as mononuclear complexes [Ag(R-pybox)2][X] [R-pybox = (S,S)-iPr-pybox and X = SbF6 (6),
PF6 (7), and BF4 (8); R-pybox = (3aS,3a′S,8aR,8a′R)-indane-pybox) and X = BF4 (9)] have been prepared by the reaction of the
corresponding silver salts and pybox ligands using the appropriate
molar ratio conditions. The first gold(I)/pybox complex [Au6Cl4{(S,S)-iPr-pybox}4][AuCl2]2 (13) has been synthesized by the reaction of [AuCl{S(CH3)2}] and (S,S)-iPr-pybox (1:1 molar ratio) in acetonitrile.
The structures of the dinuclear (1, 4, 5, 10, and 11) and mononuclear (6 and 9) silver complexes and the hexanuclear
gold complex 13 have been determined by single-crystal
X-ray diffraction analysis. These studies have been complemented with
a solution-state study by NMR spectroscopy, which included structure
elucidation, variable-temperature measurements, and diffusion studies
using diffusion-ordered spectroscopy (DOSY; for complexes 1, 4, 10, and 12). Complexes 1, 2, 4, and 10 have
been assayed as catalysts in the asymmetric addition of phenylacetylene
to N-benzylideneaniline.