On the Reactions of Bisdiolatotungsten(VI) Phenoxides. Syntheses, Characterizations, and Molecular Structures of <i>trans</i>-[WCl<sub>2</sub>(Diol)(OAr)<sub>2</sub>]
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Coordinated phenoxide groups in [W(eg)2(mephe)2] (2a) and [W(eg)2(prphe)2] (2c) (eg = ethanediolate dianion; mephe = OC6H3Me2-2,6; prphe = OC6H3iPr2-2,6) undergo reaction with Br2, leading to substitution at the para position of the phenyl rings and formation of the complexes [W(eg)2(OC6H2R2-2,6-Br-4)2] (2b, R = Me; 2d, R = iPr). The reaction of complexes 2a−2d and [W(eg)2(buphe)2] (2e) (buphe = OC6H3tBu2-2,4) with HCl leads to the displacement of one bidentate diolato ligand from the complex unit and formation of the corresponding trans dichloro diolato bis(phenoxide) tungsten(VI) complex [WCl2(eg)(OAr)2] (3). The X-ray crystal structure determinations of these compounds confirmed that all complexes 3 have a similar gross structure in which the chloro ligands are arranged at trans positions.
