We report the quantitative conversion of [M-6(IV)(mu(3)-O)(4)(mu(3)-OH)(4)Cl-12](6-) nodes in the MCl2-BTC metal organic framework into the [M-6(III)(mu(3)-O)(4) (mu(3)-ONa)(4)H-6](6-) nodes in (MH)-H-III-BTC (M = Zr, Hf; BTC is 1,3,5-benzenetricarboxylate) via bimetallic reductive elimination of H-2 from putative [M-6(IV)(mu(3)-O)(4)(mu(3)-OH)(4)H-12](6-) nodes. The coordinatively unsaturated (MH)-H-III centers in (MH)-H-III-BTC are highly active and selective for 1,4-dearomative hydroboration and hydrosilylation of pyridines and quinolines. This work demonstrated the potential of secondary building unit transformation in generating electronically unique and homogeneously inaccessible single-site solid catalysts for organic synthesis.