Preparation, Geometric and Electronic Structures of [Bi 2 Cu 4 (SPh) 8 (PPh 3 ) 4 ] with a Bi 2 Dumbbell, [Bi 4 Ag 3 (SePh) 6 Cl 3 (PPh 3 ) 3 ] 2 and [Bi 4 Ag 3 (SePh) 6 X 3 (PPh i Pr 2 ) 3 ] 2 (X = Cl, Br) with a Bi 4 Unit

BiBr 3 and CuCl react with S(Ph)SiMe 3 in thf solution in the presence of PPh 3 to yield [BiCu 2 (SPh) 3 Br 2 (PPh 3 ) 3 ] ( 1 ). The reaction of 1 with 2 equiv. of NaSPh gives rise to [Bi 2 Cu 4 (SPh) 8 (PPh 3 ) 4 ] ( 2 ) containing a Bi 2 dumbbell. In this paper we further report the synthesis and characterization of the new cluster complexes [Bi 4 Ag 3 (SePh) 6 Cl 3 (PPh 3 ) 3 ] 2 ( 3 ) and[Bi 4 Ag 3 (SePh) 6 X 3 (PPh i Pr 2 ) 3 ] 2 [X = Cl ( 4 ), Br ( 5 )]. In the surprisingly formed species 3 – 5 a formal charged Bi 4 6+ unit is observed. Compounds 3 – 5 were prepared by the reaction of BiX 3 (X = Cl, Br), AgS t Bu, Se(Ph)SiMe 3 and phosphane (PPh 3 , PPh i Pr 2 ). The structures of the compounds were determined by single‐crystal X‐ray analysis. Additionally, theoretical investigations were preformed to rationalize the bonding situation in 2 – 5 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)