New arsinidene-bridged multinuclear cluster complexes of Ag and Au. The crystal structures of [Ag-14(AsPh)(6)Cl-2(PR(3))(8)], (PR(3)=PEt(3), PMe(n)Pr(2), (PPr3)-Pr-n), [M(4)(As(4)Ph(4))(2)(PR(3))(4)], (M=Ag, PR(3)=PEt(3), (PPr)-Pr-n,; M=Au,PR(3)=(PPr3)-Pr-n),[Au-10(AsPh)(4)(PhAsSiMe(3))(2)((PPr3)-Pr-n)(6)]

The reaction of AgCl with PhAs(SiMe(3))(2) in presence of tertiary phosphines (PR(3)) leads to arsinidene-bridged silver clusters with the composition [Ag-14(AsPh)(6)Cl-2(PR(3))(8)], (PR(3)=PEt(3) 1, PMe(n)Pr(2) 2, (PPr3)-Pr-n 3). Further it is possible to obtain the multinuclear complexes [Ag-4(As(4)Ph(4))(2)(PR(3))(4)], (PR(3) = PEt(3) 4, PMe(n)Pr(2) 5). In analogy to that [PMe(3)AuCl] reacts with PhAs(SiMe(3))(2) and (PPr3)-Pr-n to form the compound [Au-4(As(4)Ph(4))(2)((PPr3)-Pr-n)(4)] 6, which is isostructurell to 4 and 5. The gold cluster [Au-10(AsPh)(4)(PhAsSiMe(3))(2)((PPr3)-Pr-n)(6)] 7 was obtained from the same solution. The structures were characterized by X-ray single crystal structure analysis.