Behavior of Organotin Sulfide Clusters towards Zinc Compounds

The reactivity of the organotin sulfide clusters [(R 1 Sn) 3 S 4 Cl] ( A , R 1 = CMe 2 CH 2 COMe) and [(R 1 Sn) 4 S 6 ] ( B ) towards different zinc chloride phosphane complexes [ZnCl 2 (PR 3 ) 2 ] as well as diphenylzinc ZnPh 2 was investigated. A diversity of different reaction products was obtained. In reactions starting from A , the tin sulfide cluster core was retained as a cation upon release of the chloride ligand, but side reactions occurred that yielded various chlorostannate or chlorozincate anions to crystallize along with the cations in the salts [(R 2 Sn) 3 S 4 ][SnCl 3 ] ( 1 , R 2 = CMe 2 CH 2 C(NNH 2 )Me), [(R 3 Sn) 3 S 4 ] 2 [dppe(ZnCl 3 ) 2 ] ( 2 , R 3 = CMe 2 CH 2 (NNHPh)Me), and [(R 2 Sn) 3 S 4 ] 2 [ZnCl 4 ] ( 3 ). In one case, transfer of the organic substituent R 3 from tin to phosphorus was observed, resulting in the phosphonium salt [R 3 PMe 3 ][HPMe 3 ][ZnCl 4 ] ( 4 ). When reacting cluster compound B with different zinc species, no zinc‐containing compounds were isolated. Instead, in one case we observed hydrolysis of B and subsequent formation of the adamantane‐type mixed oxide/sulfide cluster [(R 2 Sn) 4 S 5 O] ( 5 ), as a consequence of the Lewis acidity of ZnCl 2 . In the reaction of B with ZnPh 2 , rearrangement of the cluster was observed under transmetallation of the phenyl substituent, yielding the dinuclear complex [(R 2 PhSn) 2 S 2 ] ( 6 ).