Two new lithium chelatophosphates have been synthesized, purified, and characterized, lithium tris[3,4,5,6-tetrafluor-1,2-benzenediolato(2-)-O,O']-phosphate(1-) and lithium tris[3-fluoro-1,2-benzenediolato(2-)-O,O']-phosphate(1-). A precursor, the corresponding acid of lithium 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 analysis, when solvated by two diethyl ether molecules. The anodic oxidation limits of benzenechelatoborates and - phosphates are closely related to the energy of the highest occupied molecular orbital from semiempirical quantum-mechanical calculations with the help of QuantumCache and MOPAC 2002, yielding E-HOMO = -(3.70 +/- 0.26) x E-OX(+8.4 +/- 1.0). (C) 2003 The Electrochemical Society.