AbstractWe put forward the hypothesis that cations with 6s electrons (Hg,Tl,Pb,Bi) in the charge reservoir layers of high Tc cuprate superconductors actively participate in the pairing interaction as negative-U centers. We further argue that the Hg-cuprates are outstanding superconductors (Tc > 160 K) because they can exist as two-ion negative-U centers, . Their electrons are less localized than in single-site centers (negative-U or bipolaron) and can have a strong pairing interaction with a smaller increase in effective mass. The centers are oriented in the x and y directions and can have phase differences compatible with the d-wave symmetry of the CuO2 planes.