Bioinspired Tungsten Complexes Employing a Thioether Scorpionate Ligand.

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.