Synthese und Kristallstrukturen der Bismutchalkogenolate Bi(SC 6 H 5 ) 3 , Bi(SeC 6 H 5 ) 3 und Bi(S‐4‐CH 3 C 6 H 4 ) 3

Synthesis and Crystal Structures of Bismuth Chalcogenolato Compounds Bi(SC 6 H 5 ) 3 , Bi(SeC 6 H 5 ) 3 , and Bi(S‐4‐CH 3 C 6 H 4 ) 3 Bismuth(III) acetate reacts with thiophenol in ethyl alcohol at 80 °C to yield Bi(SC 6 H 5 ) 3 ( 1 ). Slow cool down of the deep yellow mixture lead to the formation of orange crystals of 1 . The homotype phenylselenolato compound of bismuth Bi(SeC 6 H 5 ) 3 ( 2 ) has been prepared by the reaction of BiX 3 (X = Cl, Br) with Se(C 6 H 5 )SiMe 3 in diethyl ether. In the same way as Bi(SC 6 H 5 ) 3 ( 1 ) the reaction between bismuth(III) acetate and 4‐tolulenethiole results in red crystals of Bi(S‐4‐CH 3 C 6 H 4 ) 3 ( 3 ). In consideration of three longer Bi–E distances (intermolecular interactions, E = S; Se) the Bi(EPh) 3 molecules form via face‐linked octahedra 1‐dimensional chains in the crystal lattice, while for 3 the 1‐dimensional chain is formed by face‐linked trigonal prisma. We reported herein the synthesis and structures of Bi(SC 6 H 5 ) 3 ( 1 ), Bi(SeC 6 H 5 ) 3 ( 2 ), and Bi(S‐4‐CH 3 C 6 H 4 ) 3 ( 3 ).