Bilayer architecture based on hexanuclear heterometal cluster units

An unprecedented bilayer architecture based on “head-to-head” hexanuclear heterometal clusters and linked by parallel [CuIL2] motifs has been hydrothermally made.

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]-

[PdCl2(PPh3)2] reacts with Se(SiMe3)2 to form a mixture of multinuclear Pd complexes, [Pd3Se2(SeSiMe3)2(PPh3)4] (1), [Pd5Se5(PPh3)5] (2) and [Pd8Se8(PPh3)8] (3). 1 can be used as starting material for the synthesis of further Pd clusters. Reactions of 1 with [CpCrCl2(THF)], [PdCl2(PPh3)2] and [NiCl2(PPh3)2] lead to the formation of [Pd6Se4Cl4(PPh3)6] (4), [Pd8Se8Cl(PPh3)8]+[CpCrCl3]- (5), [Pd5Se4Cl2(PPh3)6] (6) and [Pd7Se6(SeH)Cl(PPh3)7] (7). The complexes [Pd6Se4(SeH)2Cl2(PPh3)6] and [Pd6Se4(SeH)4(PPh3)6] have structures similar to 4, and are formed by reaction of [PdCl2(NBD)] or [PdCl(COD)]2(BF4)2 with PPh3 and Se(SiMe3)2.Reaction of [(C3H5)PdCl]2 with [NiCl2(PPh3)2] and S(SiMe3)2 leads to the formation of the heterometal cluster [Pd4NiS4Cl2(PPh3)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.