Molybdenum complexes of poly[(methylthio)methyl]borates

Mrózek, Ondřej; Vinklárek, Jaromı́r; Dostál, Libor; Růžičková, Zdeňka; Honzı́ček, Jan

doi:10.1016/j.poly.2018.04.036

Cited by 3 publications

(1 citation statement)

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“…Apart from scorpionate ligands, bi- or tridentate thioether ligands are equally able to provide a soft coordination sphere for metal ions, and therefore, they have been utilized in the preparation of tungsten(II) alkyne complexes of the type [WX 2 (CO)(C 2 R 2 )(L- S , S ′)] and [WX(CO)(C 2 R 2 )(L- S , S ′, S ″)]X (X = Br, I; R = Me, Ph) . In order to circumvent the limitation for a S 3 donor set and to afford a S 3 – donor for performing salt metathesis reactions, poly(thioether)borate scorpionate ligands were developed in the 1990s. , The ligand phenyltris((methylthio)methyl)borate, [PhTt], and some modifications of it are now well established in the literature with numerous complexes of Fe(II), Co(II), Ni(II), Cu(I), Zn(II), Mo(0), Mo(II), Pd(II), and Cd(II) but none of tungsten. − …”

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confidence: 99%

Bioinspired Tungsten Complexes Employing a Thioether Scorpionate Ligand

et al. 2019

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The synthesis and characterization of a series of novel tungsten complexes employing the bioinspired, sulfur-rich scorpionate ligand [PhTt] (phenyltris((methylthio)methyl)borate) are reported. Starting from the previously published tungsten precursor [WBr2(CO)3(NCMe)2], a salt metathesis reaction with 1 equiv of Cs[PhTt] led to the desired complex [WBr(CO)3(PhTt)] (1), making it the first tungsten complex employing a poly(thioether)borate ligand. Surprisingly, the reaction of [WBr2(CO)3(NCMe)2] with an excess of the ligand gave complex [W(CO)2(η2-CH2SMe)(PhTt)] (2) with a bidentate (methylthio)methanide ligand as the major product. Thereby, phenyldi((methylthio)methyl)borane is formed, which was isolated and characterized by NMR spectroscopy. The bromido ligand in [WBr(CO)3(PhTt)] was further substituted by the S,N-bidentate methimazole in order to make the first coordination sphere more sulfur-rich forming [W(CO)2(mt)(PhTt)] (3). Alkyne tungsten complexes employing the sulfur-rich scorpionate ligand were accessible by reaction of [WBr2(CO)(C2R2)2(NCMe)] (R = Me, Ph) with Cs[PhTt] forming [WBr(CO)(C2R2)2(PhTt-S,S′)] (R = Me 4, Ph 5), with the potentially tridentate ligand coordinated only via two sulfur atoms. In the case of 4, the higher flexibility of the bidentate coordination leads to the formation of two isomers with respect to the six-membered ring formed by the tungsten center and the two coordinated sulfur atoms of the ligand. All complexes 1–5 were characterized by single-crystal X-ray diffraction analysis.

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