Neue mehrkernige Pd-Komplexe mit S, Se und PPh₃ als Liganden. Die Kristallstrukturen von [Pd₅Se₄Cl₂(PPh₃)₆], [Pd₄NiS₄Cl₂(PPh₃)₆], [Pd₅Se₅(PPh₃)₅], [Pd₆Se₄Cl₄(PPh₃)₆], [Pd₇Se₆(SeH)Cl(PPh₃)₇], [Pd₈Se₈(PPh₃)₈] und [Pd₈Se₈Cl(PPh₃)₈] ⁺ [CpCrCl₃]- / New Multinuclear Pd Complexes with S, Se and PPh₃ as Ligands. The Crystal Structures of [Pd₅Se₄Cl₂(PPh₃)₆], [Pd₄NiS₄Cl₂(PPh₃)₆], [Pd₅Se₅(PPh₃)₅], [Pd₆Se₄Cl₄(PPh₃)₆], [Pd₇Se₆(SeH)Cl(PPh₃)₇], [Pd₈Se₈(PPh₃)₈] and [Pd₈Se₈Cl(PPh₃)₈]⁺[CpCrCl₃]-

Abstract

[PdCl 2 (PPh 3 ) 2 ] reacts with Se(SiMe 3 ) 2 to form a mixture of multinuclear Pd complexes, [Pd 3 Se 2 (SeSiMe 3 ) 2 (PPh 3 ) 4 ] (1), [Pd 5 Se 5 (PPh 3 ) 5 ] (2) and [Pd 8 Se 8 (PPh 3 )8] (3). 1 can be used as starting material for the synthesis of further Pd clusters. Reactions of 1 with [CpCrCl 2 (THF)], [PdCl 2 (PPh 3 ) 2 ] and [NiCl 2 (PPh 3 ) 2 ] lead to the formation of [Pd 6 Se 4 Cl 4 (PPh 3 ) 6 ] (4), [Pd 8 Se 8 Cl(PPh 3 ) 8 ] + [CpCrCl 3 ] - (5), [Pd 5 Se 4 Cl 2 (PPh 3 ) 6 ] (6) and [Pd 7 Se 6 (SeH)Cl(PPh 3 ) 7 ] (7). The complexes [Pd 6 Se 4 (SeH) 2 Cl 2 (PPh 3 ) 6 ] and [Pd 6 Se 4 (SeH) 4 (PPh 3 ) 6 ] have structures similar to 4, and are formed by reaction of [PdCl 2 (NBD)] or [PdCl(COD)] 2 (BF 4 ) 2 with PPh 3 and Se(SiMe 3 ) 2 . Reaction of [(C 3 H 5 )PdCl] 2 with [NiCl 2 (PPh 3 ) 2 ] and S(SiMe 3 ) 2 leads to the formation of the heterometal cluster [Pd 4 NiS 4 Cl 2 (PPh 3 ) 6 ] (8). The molecular structures of 2-8 show quite clearly that these compounds may be considered as intermediates on the route towards multinuclear Pd complexes.