SYNTHESIS OF SILVER(I) COMPLEXES WITH THE BIS(DIPHENYLPHOSPHANYL)-O-CARBORANE LIGAND - CRYSTAL-STRUCTURE OF [AG(PHEN)((PPH2)2C2B10H10)]CLO4 AND [AG((SPPH2)2CH2)((PPH2)2C2B10H10)]CLO4-CENTER-DOT-CH2CL2

Silver(I) perchlorate or nitrate react readily with bis(diphenylphosphanyl)-o-carborane to give the complexes [AgX{(PPh2)2C2B10H10}][X = ClO4 (1), NO3 (2)]. The perchlorate ligand is weakly bound to the silver atom and thus can be displaced by other ligands affording the three-coordinated complexes [AgL{(PPh2)2C2B10H10}]ClO4 [L = PPh3 (3), PPh2Me (4), AsPh3 (5), C5H4NCOOH (6), C9H6NCOOH (7), SPPh3 (8)]. Compounds 3 and 4 can also be obtained by reaction of [Ag(OClO3)PR3] With the diphosphane. Treatment of complex 1 with bidentate ligands leads to the cationic four-coordinated [Ag(L-L){(PPh2)2C2B10H10}]ClO4 [L-L = (PPh2)2C2B10H10 (9), bipy (10), phen (11), (SPPh2)2CH2 (12)] or to the neutral [Ag(S2CNR2){(PPh2)2C2B10H10}][NR2 = NEt2 (13), NC4H8 (14)]. The crystal structures of 11 and 12 have been established by X-ray crystallography. In both complexes the silver(I) atoms exhibit tetrahedral coordination by two phosphorus and two nitrogen or two sulfur atoms, respectively.