SYNTHESIS OF SILVER(I) COMPLEXES WITH 1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE (DPPF) - CRYSTAL-STRUCTURES OF [AG(DPPF)(PPH(3))]CLO4-CENTER-DOT-2CH(2)CL(2), [AG(DPPF)(2)]CLO4-CENTER-DOT-2CHCL(3) AND [AG(DPPF)(PHEN)]CLO4 (PHEN=1,10-PHENANTHROLINE)

Addition of 1,1'-bis(diphenylphosphino)ferrodene (dppf) to a solution of AgClO4 in 1:1 molar ratio led to the complex [Ag(OClO3)(dppf)] 1. S ubstitution of the perchlorate anion in 1 by monodentate ligands gave [Ag(dppf)(L)]ClO4 (L = PPh(3) 2 or SPPh(3) 3), or with the less steric ally demanding phosphine PPh,Me the four-do-ordinate silver(i) complex [Ag(dppf) (PPh(2)Me)(2)]ClO4 4. Direct reaction of dppf with [Ag(OClO 3)(PPh(3))] also affords complex 2. The homoleptic derivative [Ag(dppf )(2)]ClO4 5 can be synthesized by reaction of dppf and AgClO4 using a molar ratio of 2:1, or by substitution of the ClO4- by dppf in complex 1. Treatment of 1 with other bidentate ligands such as 1,10-phenanthr oline (phen), 2,2'-bipyridine (bipy) or bis (diphenylphosphino) methan e disulfide (SdppmS) gave mixed cationic four-co-ordinate complexes [A g(dppf)(L-L)]ClO4 (L-L = phen 6, bipy 7 or SdppmS 8); with sodium dith iocarbamates Na(S(2)CNR(2)) the neutral species [Ag(S(2)CNR(2))-(dppf) ] (R = Et 9 or Me 10) were obtained. The crystal structures of complex es 2, 5 and 6 have been established by X-ray diffraction. Compound 2 s hows a trigonal-planar silver(I) centre, whereas in complexes 5 and 6 the silver atom exhibits a tetrahedral geometry.