The ligand [Cp 2MoH 2] in complexes with AgS bonds

Abstract

The reaction of [Cp 2MoH 2] and AgBF 4 with the dithio-ligands Na(S 2CNR 2) (R=Et, Ph), Na(S 2CMe), NH 4(S 2P(OEt) 2) and K(S 2CO i Pr) gives the complexes [(Cp 2MoH 2AgS 2CNR 2) 2] (R=Et 1, Ph 2), [(Cp 2MoH 2AgS 2CMe) 2] ( 3), [(Cp 2MoH 2AgS 2P(OEt) 2) 2] ( 4) and [(Cp 2MoH 2AgS 2CO i Pr) n ] ( 6) with probably n=2, all with a [Cp 2MoH 2]:Ag:dithio-ligand stoichiometry of 1:1:1. 1– 4 form dimers in which two dithio-ligands bridge two silver atoms. In 1 and 2 one sulphur atom is coordinated to one silver atom, whereas the other is coordinated to both silver atoms. In 3 and 4 each sulphur atom is bonded to one silver atom only. In 1– 3 there is a silversilver bond. However, in 4 the Ag⋯Ag distance is too long for an AgAg bond. Crystallization of the compound 6 afforded a polymer [(Cp 2MoH 2Ag 4(S 2CO i Pr) 4) n ] ( 7) with a stoichiometry [Cp 2MoH 2]:Ag:dithio-ligand=1:4:4. The polymer forms sheets with rings surrounding a [Cp 2MoH 2] ligand bonded to one of the four silver atoms. The monomer [(Cp 2MoH 2) 2AgS 2COEt] ( 5) with a stoichiometry [Cp 2MoH 2]:Ag:dithio-ligand=2:1:1 was prepared by addition of Na(S 2COEt) to [Cp 2MoH 2] and AgBF 4. In 5 the xanthogenate ligand is bonded with both sulphur atoms to the silver atom. The compounds 1– 6 were characterized analytically and spectroscopically. The structures of 1– 5 and 7 were determined by single crystal X-ray analyses.