Charles G. Schmid

Oxygen- and Sulfur-Capped Organotin Clusters

Abstract The synthesis and structural features of the oxygen-capped cluster, [(n-BuSn(OH)O2P (OBut)2)3O] [O2P(OBut)2] (l), are compared to that of the analogous formulations containing framework sulfur atoms in place of oxygens, [(n-BuSn(S) (OH)OP(OBut)2)3S] [O2P(OBut)2]·2H2S·H2O (2) and [(n-BuSn)3(S)(O)(O2CPh)5] (3). Solution NMR, 119Sn and 31P, indicate that the solid state structures determined by X-ray analysis are retained in solution.

A New Heptanuclear Tin Cluster Containing Sulfur and Oxygen in the Framework

Abstract We have recently reported that new structural forms having the cube, (n-BuSn(O)O2PPh2)4, and oxygen-capped, [(n-BuSn(OH)O2PPh2)3O] [O2PPh2], formulations can be prepared by the reaction of n-butylstannonic acid with the corresponding diorganophosphinic acid. In new work exploring the effects of the bulky mesityl group bound to phosphorus, a cube formulation was also obtained. When n-butylstannonic acid was reacted with dicyclohexylphosphinic acid in the presence of nitric acid an oxygen-capped cluster having nitrate as the anion was obtained, demonstrating that the phosphinate anion is not required to stabilize the o-capped cation. In an attempt to generate similar structural forms, with sulfur replacing oxygen in the framework, the reaction of n-butylstannonic acid with diphenylphosphine oxide in the presence of elemental sulfur has been explored. From this reaction, a new structural form, containing seven hexacoordinate tin atoms and incorporating sulfur into the framework, [(n-BuSn(S)O2PPh2)3O...