A diverse array of structures for the complexes of silver(I) halide with triphenylphosphine (PPh3) has beenstudied. The complexes may be described as being of the type [AgX(PPh3)n] (X = Cl, Br or I). The value of n varies inthe range of 1-3. This also indicates that the stoichiometry of the complexes is in the range of 1-3. The complex withstoichiometry 1:1 is a tetramer. There are two structural types of tetramer reported, termed cubane and step or chair. Thecubane structure has been reported for [AgX(pPh3)]4ex = Cl, Br or I), while the step structure has only been reported for[AgI(PPh3)]4' The complex with stoichiometry 1:2 may be a monomer or a dimer. The monomer has a quasi trigonalplanar structural type and has only been reported for [AgBr(PPh3)2l The dimer has been reported for [(PPh3)2Ag(J.!-X)2Ag(PPh3)2](X = Cl or Br) with silver atom in the distorted tetrahedral environment. The complex with stoichiometry1:3 has a distorted tetrahedral structural type and has been reported for [AgX(PPh3)3](X = Cl, Br or I). Changing PPh3with more hindered ligand such as tricyclohexylephosphine (PCY3)or derivative of PPh3 such as diphenyl-2,4,6-trimethoxy(phenyl)phosphine (dpmp), phenyl-bis{2,4,6-trimethoxy(phenyl)} phosphine (pdmp), or tris{2,4,6-trimethoxy(phenyl)}phosphine (tmpp) may give complexes with various structural types but with lower range ofstoichiometry. Synthesis and X-ray structural study of these complexes has been done with the results summarizedbelow. Silver(I) halide and PCY3give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 isa dimer or cubane. The dimer is observed for [(PcY3)Ag(J.!-X)2Ag(PCY3)] ex = Cl or Br). The unusual dimer is observedfor [(PcY3)Ag(J.!-IMJ.!-py)Ag(PCY3)] where the pyridine ligand is bonded to two silver atoms. The cubane is observed for[AgI(PCY3)J4,The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for[AgX(PCY3)2]ex = Cl, Br, I). Silver(I) halide and dpmp give complexes with stoichiometry 1:1 and 1:2. The complexwith stoichiometry 1:1 is a dimer and has been observed for [(dpmp)Ag(J.!-X)2Ag(dpmp)]ex = Cl, Br or I). The complexwith stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(dpmp)2] (X = Cl, Br,I). Silver(I) halide and pdmp also give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 isa dimer and has been observed for [(pdmp)Ag(J.!-X)2Ag(pdmp)](X = CI, Br or I). The complex with stoichiometry 1:2has a quasi trigonal planar structural type and has been observed for [AgX(pdmp)2] (X = CI, Br, I). Silver(I) halide andtmmp only give complexes with stoichiometry I: I. This complex is a monomer and has been observed for [AgX(tmpp)](X = Cl or Br). In this complex the silver atom is in a quasi linear environment. Based on the bond lengths betweensilver and phosphorous atoms in the complexes obtained, it can be concluded that bulky ligands tend to give complexeswith lower range of stoichiometry. In addition, the bulkier the ligand the longer the bond length between the silver andphosphorous atoms. Effendy1 and A. H. White2/Jurusan Kimia, FMIPA Universitas Negeri Malang, Jl. Surabaya 6Malang 65145, Indonesia2 Chemistry, School of Biomedical, Biomolecular, and Chemical Sciences, The University of WesternAustralia, 35 Stirling Highway, Crawley WA 6009, Australia
