The reactivity of the intramolecularly coordinated organotin-(IV) carbonate L(Ph)Sn(CO 3 ) (1), where L stands for an N,C,N-chelating ligand, 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 , was studied. The treatment of 1 with ferrocene-based carboxylic acids RCOOH afforded the organotin(IV) dicarboxylates LPhSn(O 2 CR) 2 , where R is ferrocenyl (2), 2-ferrocenylethyl (3), and [(1E)-2-ferrocenyl]ethenyl (4). Surprisingly, compounds 2−4 are sensitive to moisture and easily hydrolyze with condensation into the corresponding hexameric organotin oxo clusters (PhSnO) 6 (O 2 CR) 6 (R = ferrocenyl (5), 2-ferrocenylethyl (6), and [(1E)-2-ferrocenyl]ethenyl ( 7)) possessing a Sn 6 O 6 drumlike core. On the other hand, treatment of 1 with non-carboxylic acids such as HOTf, H 3 BO 3 , H 3 PO 3 , and t-BuPO 3 H 2 afforded the triflate salt of a cationic organotin(IV 9), and organotin(IV) phosphite [L(Ph)Sn(HPO 3 )] 2 (10) and phosphonate {[L(Ph)Sn] 2 (μ-OH 2 )(μ-t-BuPO 3 ) 2 } (11), respectively. Compounds 2−11 were characterized by elemental analysis and multinuclear NMR spectroscopy, and the molecular structures of compounds 6 and 9−11 were determined by single-crystal Xray diffraction analysis. In addition, compounds 2−7 bearing redox-active ferrocenyl groups were studied by cyclic voltammetry.