On the reactions of bisdiolatotungsten(VI) phenoxides. Syntheses, characterizations, and molecular structures of trans-[WCl(2)(Diol)(OAr)(2)].
Coordinated phenoxide groups in [W(eg)(2)(mephe)(2)] (2a) and [W(eg)(2)(prphe)(2)] (2c) (eg = ethanediolate dianion; mephe = OC(6)H(3)Me(2)-2,6; prphe = OC(6)H(3)(i)Pr(2)-2,6) undergo reaction with Br(2), leading to substitution at the para position of the phenyl rings and formation of the complexes [W(eg)(2)(OC(6)H(2)R(2)-2,6-Br-4)(2)] (2b, R = Me; 2d, R = (i)Pr). The reaction of complexes 2a-2d and [W(eg)(2)(buphe)(2)] (2e) (buphe = OC(6)H(3)tBu(2)-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 [WCl(2)(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.
Lehtonen
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Department of Chemistry, University of Turku, FIN-20014, Turku, Finland. ari.lehtonen@utu.fi
Sillanpää
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