Synthesis, Structure, and Catalytic Properties of VIV, MnIII, MoVI, and UVI Complexes Containing Bidentate (N, O) Oxazine and Oxazoline Ligands
Authors:
- 3 August 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 43 (18) , 5704-5713
Abstract
Synthesis of seven complexes containing oxazoline {[(L1)2VO] (4), [(L1)2MoO2] (5), [(L1)2UO2] (6); HL1 (1) [HL1 = 2-(4‘,4‘-dimethyl-3‘-4‘-dihydroxazol-2‘-yl)phenol]}, chiral oxazoline {[(L2)2UO2] (7); HL2 (2) [HL2 = (4‘R)-2-(4‘-ethyl-3‘4‘-dihyroxazol-2‘-yl)phenol]}, and oxazine {[(L3)2VO] (8), [(L3)2Mn(CH3COO-)] (9), [(L3)2Co] (10); HL3 (3) [HL3 = 2-(5,6-dihydro-4H-1,3-oxazolinyl)phenol]} and their characterization by various techniques such as UV−vis, IR, and EPR spectroscopy, mass spectrometry, cyclic voltammetry, and elemental analysis are reported. The novel oxazine (3) and complexes 4, 5, 8 and 9 were also characterized by X-ray crystallography. Oxazine 3 crystallizes in the monoclinic system with the P21/n space group, complexes 4 and 9 crystallize in the monoclinic system with the P21/c space group, and complexes 5 and 8 crystallize in the orthorhombic system with the C2221 space group and the P212121 chiral space group, respectively. The representative synthetic procedure involves the reaction of metal acetate or acetylacetonate derivatives with corresponding ligand in ethanol. Addition of Mn(OAc)2·4H2O to an ethanol solution of 3 gave the unexpected complex Mn(L3)2·(CH3COO-) (9) where the acetate group is coordinated with the metal center in a bidentate fashion. The catalytic activity of complexes 4−9 for oxidation of styrene with tert-butyl hydroperoxide was tested. In all cases, benzaldehyde formed exclusively as the oxidation product.Keywords
This publication has 48 references indexed in Scilit:
- Erratum to “4-Ferrocenyl-1,3-oxazoline derivatives as ligands for catalytic asymmetric allylation reactions”: [Journal of Organometallic Chemistry 660 (2002) 62–70]Journal of Organometallic Chemistry, 2003
- Manganese Oxidation Catalysts with 2-(2′-Hydroxyphenyl)oxazoline Ligands: Catalyst Intermediates and Degradation Products − Crystal Structure of Bis[{2-(2′-oxazolinyl)phenolato}bis(1-methylimidazole)manganese(III)] PerchlorateEuropean Journal of Inorganic Chemistry, 2002
- Electrochemical and Catalytic Properties of Novel Manganese(III) Complexes with Substituted 2-(2′-Hydroxyphenyl)oxazoline Ligands − X-ray Structures of Tris[5-methyl-2-(2′-oxazolinyl)phenolato]manganese(III) and Tris[5-chloro-2-(2′-oxazolinyl)phenolato]manganese(III)European Journal of Inorganic Chemistry, 2002
- Chiral dioxomolybdenum(VI) complexes for enantioselective alkene epoxidationJournal of Organometallic Chemistry, 2001
- First Dioxomolybdenum(VI) Complexes Containing Chiral Oxazoline Ligands: Synthesis, Characterization and Catalytic ActivityEuropean Journal of Inorganic Chemistry, 2001
- 2-(4′,4′-Dimethyl-3′,4′-dihydrooxazol-2′-yl)phenol: Some First-Row Transition Metal Complexes of This Naturally Occurring Binding GroupEuropean Journal of Inorganic Chemistry, 2001
- Design of Chiral Ligands for Asymmetric Catalysis: from C2-Symmetric Semicorrins and Bisoxazolines to Non-Symmetric Phosphinooxazolines.Acta Chemica Scandinavica, 1996
- (Hydroxyphenyl)oxazoline: a Novel and Remarkably Facile Entry into the Area of Chiral Cationic Alkylzirconium Complexes Which Serve as Polymerization CatalystsOrganometallics, 1995
- Chiral semicorrins and related nitrogen heterocycles as ligands in asymmetric catalysisAccounts of Chemical Research, 1993
- Molybdenum(VI)-dioxo complexes with linear and tripodal tetradentate ligands: models for the molybdenum(VI/V) centers of the molybdenum hydroxylases and related enzymes. 1. Syntheses and structuresInorganic Chemistry, 1989