Ivanova S M, Nolan B G, Kobayashi Y, Miller S M, Anderson O P, Strauss S H
Department of Chemistry, Colorado State University, Ft. Collins 80523, USA.
Chemistry. 2001 Jan 19;7(2):503-10. doi: 10.1002/1521-3765(20010119)7:2<503::aid-chem503>3.0.co;2-1.
The relative Lewis basicities of six Al(ORF)4- ions, Al[OC(CH3)(CF3)2]4-, Al(OC(CF3)3]4-, Al(OCPh(CF3)2]4-, Al[OC4-C6H4(tBu)2]4-, Al(OC(Cy)(CF3)2]4-, and Al(OCPh2(CF3)]4-, have been determined by measuring their relative coordinating abilities towards Li+ in dichloromethane. The relative Li- Lewis basicities of the Al(ORF)4- ions are linearly related to the aqueous pKa values of the corresponding parent HORF fluoroalcohols. The Lewis basicity of Al[OCH(CF3)2]4- could not be measured because two of these anions can coordinate to one Li+ cation. The structures of LiAl[OCH(CF3)2]4 and [1-Et-3-Me-1,3-C3H3N2][Li[Al[OCH(CF3)2)4]2] were determined.
通过测量六种Al(ORF)₄⁻离子，即Al[OC(CH₃)(CF₃)₂]₄⁻、Al(OC(CF₃)₃]₄⁻、Al(OCPh(CF₃)₂]₄⁻、Al[OC4-C₆H₄(tBu)₂]₄⁻、Al(OC(Cy)(CF₃)₂]₄⁻和Al(OCPh₂(CF₃)]₄⁻在二氯甲烷中对Li⁺的相对配位能力，确定了它们的相对路易斯碱度。Al(ORF)₄⁻离子的相对Li⁺路易斯碱度与相应母体HORF氟代醇的水相pKa值呈线性相关。由于其中两个阴离子可以与一个Li⁺阳离子配位，因此无法测量Al[OCH(CF₃)₂]₄⁻的路易斯碱度。确定了LiAl[OCH(CF₃)₂]₄和[1-Et-3-Me-1,3-C₃H₃N₂][Li[Al[OCH(CF₃)₂)₄]₂]的结构。
