Publications

Structural diversity in lithium aryloxides, Part 2

Boyle, Timothy J.; Alam, Todd M.; Rodriguez, Marko A.

A series of arylalcohols [H-OAr where OAr = OC{sub 6}H{sub 5} (OPh), OC{sub 6}H{sub 4}(2-Me) (oMP), OC{sub 6}H{sub 3}(2,6-Me){sub 2} (DMP), OC{sub 6}H{sub 4}(2-Pr{prime}) (oPP), OC{sub 6}H{sub 3}(2,6-Pr{prime}){sub 2} (DIP), OC{sub 6}H{sub 4}(2-Bu{prime}) (oBP), OC{sub 6}H{sub 3}(2,6-Bu{prime}){sub 2} (DBP) where Me = CH{sub 3}, Pr{prime} = CHMe{sub 2}, and Bu{prime} = CMe{sub 3}] were reacted with LiN(SiMe{sub 3}){sub 2} in pyridine (py) to generate the appropriate ``Li(OAr)(py){sub x}'' complex. The resultant products were characterized by single crystal X-ray diffraction as: [Li(OPh)(py){sub 2}]{sub 2} (1), [Li(oMP)(py){sub 2}]{sub 2} (2), [Li(DMP)(py){sub 2}]{sub 2} (3), [Li(oPP)(py){sub 2}]{sub 2} (4), [Li(DIP)(py){sub 2}]{sub 2} (5), [Li(oBP)(py){sub 2}]{sub 2} (6), and [Li(DBP)(py)]{sub 2} (7). Compounds 1--6 adopt a dinuclear, edge-shared tetrahedral complex. For 7, due to the steric crowding of the DBP ligand, only one py is coordinated yielding a dinuclear fused trigonal planar arrangement. Two additional structure types were also characterized for the DIP ligand as [Li(DIP)(H-DIP)(py)]{sub 2} (5b) and [Li{sub 2}(DIP){sub 2}(py){sub 3}] (5c). {sup 6,7}Li and {sup 13}C NMR solid state MAS spectroscopy indicated that the bulk powder was consistent with the crystalline material. Solution state NMR spectroscopy revealed a symmetric molecule existed in solution for 1--7.