Zinc(II) complexes with fluorinated monodentate aryloxide and alkoxide ligands

The monomeric and dimeric Zn(II) aryloxide complexes {K(18C6)}2[Zn(OArF)4], 1a, {K(18C6)}[KZn(OArF)4], 1b, {K(18C6)}2[Zn(OAr′)4], 2a, {K(18C6)}2[Zn2(OArF)6], 3, including a heterobimetallic Zn–Tl complex [Tl2Zn(OArF)4], 4, and the first homoleptic, mononuclear Zn(II) alkoxide complex {K(18C6)}[Zn(OCPhMeF2)3], have been prepared and characterized by 1H, 13C{1H}, 19F NMR spectroscopy as well as single crystal X-ray diffraction, including one alternative crystal structure {K(18C6)}2[Zn(OAr′)4]·toluene, 2b, from different recrystallization conditions. A detailed structural comparison to other Zn aryloxide and alkoxide complexes in the literature is presented which shows the same general pattern of increased Zn–O bond lengths with fluorinated ligands compared to very similar structures in non-fluorinated analogs. Compound 4 also exhibits Tl⋯arene bonding in the solid state.

Graphical abstractMonomeric and dimeric Zn(II) aryloxide compounds and the first homoleptic, mononuclear Zn(II) alkoxide complex have been prepared and compared with related literature compounds without extensive ligand fluorination.Figure optionsDownload full-size imageDownload as PowerPoint slide