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Evidence for high-Tc cuprate superconductivity is found in a region of the phase diagram where non-superconducting Fermi liquid metals are expected. Cu valences estimated independently from both x-ray absorption near-edge spectroscopy and bond valence sum measurements are >2.3, and are in close agreement with each other for structures in the homologous series (Cu0.75Mo0.25)Sr2(Y,Ce)sCu2O5+2s+δ with s = 1, 2, 3, and 4. The record short apical oxygen distance, at odds with current theory, suggests the possibility of a new pairing mechanism. The possibility that the charge reservoir layers are able to screen long range coulomb interactions and thus enhance Tc is discussed.