Acid- or Base-Induced Rearrangements of Ferrocenyl-Decorated Organotin Sulfide Cages

Treatment of keto-functionalized organotin sulfide [((RSn)-Sn-1)(4)S-6] {A; R-1 = C(Me)(2)CH2C(Me) O} or its derivative [((RSn)-Sn-fC1)(4)S-6] {B, R-fC1 = fC[C(O) NH-N=(Me) CCH2(Me)(2)C](2)} with acids or bases leads to a variety of novel organo-functionalized tin sulfide/oxide cages. In addition to rearrangements of the inorganic core, the compounds comprise different organic decorations with ligands R-2 = C(Me)(2)CH2C(Me)= N-NH2, R-fC2 = [C(Me)(2)CH2C(Me)= N-NHC(O)] fC[C(O-)= N-N= C-(Me) CH2(Me)(2)C], R-fC3 = fC[C(O-)= N-N= C(Me)CH2(Me)(2)C](2), R-fC4 = [C(Me)(2)CH2C(Me)= N-NHC(O)]fC[C(O) NH-NH2], and R-fCO = [fC(COO)(2)](2-). We show how the reaction conditions influence the course of the reactions and hence the nature of the products, among them a series of mixed-valent complexes based on [Sn-II(Sn-IV)(2)S-4] defect-heterocubane units.