SYNTHESIS AND STRUCTURE OF cis-syn-[Cd(μ-SEt)(S2CSEt)(P{c-C6H11}3)]2

Synthesis, X-ray Diffraction, NMR and Thermolysis Studies of Cadmium Tin Sulfido Complexes

“…This is the typical structural motive for cadmium sulfide thiolate cluster molecules [63]. Bond distances in the core are similar to literature values of that motif varying from 247.5(9) pm to 252.8 (9) pm and are also similar to Cd-S distances in both CdS modifications with distances of 252.5 pm to 254.0 pm. For the peripheral cadmium atoms Cd1 and Cd2 the distances vary from 243(2) pm to 262.2(9) pm, probably due to steric interactions of the phosphine ligands and the SnPh 2 groups.…”

“…Four cadmium atoms (Cd3, Cd2 and symmetry equivalent atoms) bind to sulfur atoms only, while three cadmium atoms (Cd1) bind to three sulfur atoms and one i Pr 3 P ligand. The Cd-P distance (262(2) pm) is in the same range as observed for phosphine stabilized cadmium thiolate complexes [9,10,62]. Six tin atoms are located in the outer sphere of the CdS core which are coordinated by two sulfur atoms and two phenyl groups.…”

“…(9) pm) and in good agreement with Sn-S distances in copper tin sulfido complexes[56,59,60]. S-Sn-S bond angles (103.55(3)° for Sn1 and 107.79(3)° for Sn2) are smaller than the ideal tetrahedral angle.…”

“…Suitable starting materials for the solution-based synthesis of cadmium tin sulfido complexes are cadmium chalcogenolate complexes which are known in the literature with different ligands coordinating the Cd 2+ ions, e.g., tmeda-stabilized chalcogenolates [3][4][5][6][7]. Moreover, tertiary phosphine ligands have been used to synthesize complexes such as [Cd 4 (SPh) 6 (PPh 3 ) 4 ](ClO 4 ) 2 [8], [Cd(SEt)(S 2 CSEt)(P{c-hex} 3 )] 2 [9] or [Cd 17 S 4 (SH) 2 (SPh) 24 (PPh 3 ) 2 ] [10] (Et = C 2 H 5 , Ph = C 6 H 5 , c-hex = cyclo-C 6 H 11 ) and also a mixed zinc-cadmium thiophenolate complex [11].…”