Synthesis and Electrochemical Properties of Some Lithium Chelatophosphates

Abstract

Two new Li chelatophosphates were synthesized, purified, and characterized, Li tris[3,4,5,6-tetrafluor-1,2-benzenediolato(2-)-O,O']-phosphate(1-) and Li tris[3-fluoro-1,2-benzenediolato(2-)-O,O']-phosphate(1-). A precursor, the corresponding acid of Li tris[3,4,5,6-tetrafluor-1,2-benzenediolato(2-)-O,O']-phosphate(1-), H+[P(C6F4O2)3]-, presumably a super acid, shows a hexacoordinated phosphorous in x-ray anal., when solvated by two Et2O mols. The anodic oxidn. limits of benzenechelatoborates and -phosphates are closely related to the energy of the HOMO from semiempirical quantum-mech. calcns. with the help of QuantumCache and MOPAC 2002, yielding EHOMO = -(3.70 ± 0.26)×EOX(+8.4 ± 1.0).