期刊
POLYHEDRON
卷 26, 期 12, 页码 2559-2568出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2006.12.032
关键词
vanadium(V); Schiff base; complexes
New dioxovanadium(V) complexes bearing tridentate products of single condensation of RR(-) and of SS(+)-1,2-diaminocyclohexane with salicylaldehyde and its derivatives, 2-hydroxy-1-n,aphthaldehyde and 1-hydroxy-2-acetonaphthone, have been synthesized. The crystal structure of the {RR(-)-1-amino-2-N-[1 '-(1 ''-oxido-kappa O-2 ''-naphthyl)ethylidene]aminocyclohexane-kappa(2) N}dioxovanadium(V) hemihydrate hemiethanol solvate, determined by X-ray analysis, is characterized by trigonal bipyramidal coordination geometry of complex molecules which are linked to solvent molecules by hydrogen bonds to form chains. The cyclohexane ring is in chair conformation with a very small distortion towards half-chair and envelope forms. Complexes were characterized by UV-Vis, FTIR, H-1, C-13, V-51 NMR and CD spectroscopies. CD spectra of {RR(-)-1-arnino-2-N-[(2 '-oxido-kappa O-5 '-nitrophenyl)methylene]aminocyclohexane-kappa(2) N} dioxovanadium(V) and of R(-)-1,2-diaminopropane analogue do not bear mirror image relationship in contrast to V(IV and V), Cu(II) and Ni(II) complexes containing double condensed diamines in the same absolute configurations. H-1 and C-13 NMR resonance signals of all complexes dissolved in DMSO were assigned. The complexes bearing the methoxy substituent in position 3 or 5 of the aryl group catalyse the oxidation of methyl phenyl sulfide by cumene hydroperoxide to the corresponding sulfoxide with reasonable enantiomeric excesses (19-23%). (c) 2007 Elsevier Ltd. All rights reserved.
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