Syntheses and crystal structures of [Cu-4(As4Ph4)(2)(PRR '(2))(4)], [Cu-14(AsPh)(6)(SCN)(2)(PEt2Ph)(8)], [Cu-14(AsPh)(6)Cl-2(PRR '(2))(8)], [Cu-12(AsPh)(6)(PPh3)(6)], [Cu-10(AsPh)(4)Cl-2(PMe3)(8)], [Cu-12(AsSiMe3)(6)(PRR '(2))(6)], and [Cu-8(AsSiMe3)(4)((PBu3)-Bu-t)(4)] (R, R ' = organic groups)

Through the reaction of CuSCN with AsPh(SiMe3)(2) in the presence of tertia ry phosphines the compounds [Cu-4(As4Ph4)(2)(PRR'(2))(4)] (1-3) (1: R=R'=Pr -n, 2. R = R' = Et; 3: R = Me, R' = Pr-n) and [Cu-14(ASPh)(6)(SCN)(2)- (PEt 2Ph)(8)] (4) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu-14(AsPh)(6)Cl-2(PRR'(2))(8)] (5-6) (5: R = R' = Et; 6: R = Me, R'=Pr-n), [Cu-12(AsPh)(6)(PPh3)(6)] (7) and [Cu-10(AsPh)(4)Cl-2( PMe3)(8)] (8). Through reactions of CuOAc with As(SiMe3)(3) in the presence of tertiary phosphines the compounds Cu-12(AsSiMe3)(6)(PRR'(2))(6)] (9-11) (9: R = R' = Et; 10: R = Ph, R' = Et; 11: R = Et, R' = Ph) and [Cu-8(AsSiM e3)(4)((PBu3)-Bu-t)(4)] (12) can be obtained. In each case the products wer e characterised by single-crystal-X-ray-structure-analyses. As the main str ucture element 1-3 each have two As4Ph42--chains as ligands. In contrast 4- 12 contain discrete AsR2--ligands.