A1 Refereed original research article in a scientific journal
Reactions of tris(ethanediolato)tungsten and tungsten oxytetrachloride with aminotris(phenol)s: Alkoxide, chloro, and alkyl derivatives of oxotungsten(VI) complexes with tetradentate [O3N]-type ligands
Authors: Lehtonen A, Sillanpaa R
Publisher: AMER CHEMICAL SOC
Publication year: 2005
Journal:: Organometallics
Journal name in source: ORGANOMETALLICS
Journal acronym: ORGANOMETALLICS
Volume: 24
Issue: 11
First page : 2795
Last page: 2800
Number of pages: 6
ISSN: 0276-7333
DOI: https://doi.org/10.1021/om050103w
Abstract
Trisdiolatotungsten(VI) complex [W(eg)(3)] (eg = 1,2-ethanediolato dianion) reacts in refluxing toluene solution with phenolic ligand precursors tris(2-hydroxy-3,5-dimethylbenzyl)amine (H3LMe) and tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine (H3LtBu) to form monomeric oxotungsten(VI) complexes [WO(L-Me)(Heg)] and [WO(L-tBu)(Heg)], respectively. These complexes undergo chloride-for-alkoxide substitution when treated with SOCl2 in CH2Cl2, which leads to the formation of corresponding chloro complexes [WO(LMe)Cl] and [WO-(L-tBu)cl]. Identical chloro complexes are also formed in the reaction between these phenolic ligand precursors and [WOCl4]. The reaction of [WO(L-R)Cl] complexes with Grignard reagents yields corresponding monoalkyl derivatives [WO(L-R)(Me)] and [WO(L-R)(CH2CMe2Ph)]. These alkyl derivatives are stable in ambient atmosphere. All new compounds are mononuclear molecules, in which the tripodal aminotris(phenolate) group has coordinated as a tetradentate ligand through three oxygen donors and one nitrogen donor, whereas the nitrogen donor is located trans to the terminal oxo group.
Trisdiolatotungsten(VI) complex [W(eg)(3)] (eg = 1,2-ethanediolato dianion) reacts in refluxing toluene solution with phenolic ligand precursors tris(2-hydroxy-3,5-dimethylbenzyl)amine (H3LMe) and tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine (H3LtBu) to form monomeric oxotungsten(VI) complexes [WO(L-Me)(Heg)] and [WO(L-tBu)(Heg)], respectively. These complexes undergo chloride-for-alkoxide substitution when treated with SOCl2 in CH2Cl2, which leads to the formation of corresponding chloro complexes [WO(LMe)Cl] and [WO-(L-tBu)cl]. Identical chloro complexes are also formed in the reaction between these phenolic ligand precursors and [WOCl4]. The reaction of [WO(L-R)Cl] complexes with Grignard reagents yields corresponding monoalkyl derivatives [WO(L-R)(Me)] and [WO(L-R)(CH2CMe2Ph)]. These alkyl derivatives are stable in ambient atmosphere. All new compounds are mononuclear molecules, in which the tripodal aminotris(phenolate) group has coordinated as a tetradentate ligand through three oxygen donors and one nitrogen donor, whereas the nitrogen donor is located trans to the terminal oxo group.
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