4.5 Article

Molybdenum(VI) complexes with a chiral L-alanine bisphenol [O,N,O,O'] ligand. Synthesis, structure, spectroscopic properties and catalytic activity

Journal

INORGANICA CHIMICA ACTA
Volume 553, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2023.121519

Keywords

Molybdenum; L-alanine; Epoxidations; Catalysis

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Dioxidomolybdenum(VI) compound [MoO2Cl2(dmso)(2)] reacts with a chiral tetradentate O3N-type L-alanine bisphenol ligand precursor (Et3NH)H2Lala to form an oxidochloridomolybdenum(VI) complex [MoOCl(L-ala)] (1) as two separable geometric isomers with phenolate groups in cis or trans positions. The single crystal X-ray and NMR analyses of cis- and trans-1 reveal that the complexes are formed of monomeric molecules, in which the ligand has a tetradentate coordination through three oxygen donors and one nitrogen donor. The reaction of Na2MoO4 center dot 2H(2)O with the same ligand precursor in an acidic methanol solution leads to the formation of an anionic dioxido complex (Et3NH)[MoO2(L-ala)] (2) with a trans coordination of the tetradentate ligand. Trans-1 and 2 were studied as active catalysts for olefin epoxidation: i.e. styrene, cyclohexene, S(-)-limonene and (-)-alpha-pinene using H2O2 and tBuOOH as oxidants.
Dioxidomolybdenum(VI) compound [MoO2Cl2(dmso)(2)] reacts with a chiral tetradentate O3N-type L-alanine bisphenol ligand precursor (Et3NH)H2Lala to form an oxidochloridomolybdenum(VI) complex [MoOCl(L-ala)] (1) as two separable geometric isomers with phenolate groups in cis or trans positions. The single crystal X-ray and NMR analyses of cis- and trans-1 reveal that the complexes are formed of monomeric molecules, in which the ligand has a tetradentate coordination through three oxygen donors and one nitrogen donor. The reaction of Na2MoO4 center dot 2H(2)O with the same ligand precursor in an acidic methanol solution leads to the formation of an anionic dioxido complex (Et3NH)[MoO2(L-ala)] (2) with a trans coordination of the tetradentate ligand. Trans-1 and 2 were studied as active catalysts for olefin epoxidation: i.e. styrene, cyclohexene, S(-)-limonene and (-)-alpha-pinene using H2O2 and tBuOOH as oxidants.

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