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Title: Synthesis and X-ray Structural Study on the Complexes of Silver(I) Halide with Tricyclohexylephosphine, Diphenyl-(2,4,6-trimethoxy)phenylphosphine, Phenyl-2,4,6-trimethoxyphenyl phosphine, and Tris(2,4,6-trimethoxy)phenylphosphine

Abstract

A diverse array of structures for the complexes of silver(I) halide with triphenylphosphine (PPh{sub 3}) has been studied. The complexes may be described as being of the type [AgX(PPh{sub 3}){sub n}] (X = Cl, Br or I). The value of n varies in the range of 1-3. This also indicates that the stoichiometry of the complexes is in the range of 1-3. The complex with stoichiometry 1:1 is a tetramer. There are two structural types of tetramer reported, termed cubane and step or chair. The cubane structure has been reported for [AgX(PPh{sub 3})]{sub 4} (X = Cl, Br or I), while the step structure has only been reported for [AgI(PPh{sub 3})]{sub 4}. The complex with stoichiometry 1:2 may be a monomer or a dimer. The monomer has a quasi trigonal planar structural type and has only been reported for [AgBr(PPh{sub 3}){sub 2}]. The dimer has been reported for [(PPh{sub 3}){sub 2}Ag({mu}-X){sub 2}Ag(PPh{sub 3}){sub 2}] (X = Cl or Br) with silver atom in the distorted tetrahedral environment. The complex with stoichiometry 1:3 has a distorted tetrahedral structural type and has been reported for [AgX(PPh{sub 3}){sub 3}] (X = Cl, Br or I). Changing PPh{sub 3} with more hindered ligand suchmore » as tricyclohexylephosphine (Pcy{sub 3}) or derivative of PPh{sub 3} such as diphenyl-2,4,6-trimethoxy(phenyl)phosphine (dpmp), phenyl-bis{l_brace}2,4,6-trimethoxy(phenyl){r_brace} phosphine (pdmp), or tris{l_brace}2,4,6-trimethoxy(phenyl){r_brace}phosphine (tmpp) may give complexes with various structural types but with lower range of stoichiometry. Synthesis and X-ray structural study of these complexes has been done with the results summarized below. Silver(I) halide and Pcy{sub 3} give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 is a dimer or cubane. The dimer is observed for [(Pcy{sub 3})Ag({mu}-X){sub 2}Ag(Pcy{sub 3})] (X = Cl or Br). The unusual dimer is observed for [(Pcy{sub 3})Ag({mu}-I){sub 2}({mu}-py)Ag(Pcy{sub 3})] where the pyridine ligand is bonded to two silver atoms. The cubane is observed for [AgI(Pcy{sub 3})]{sub 4}. The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(Pcy{sub 3}){sub 2}] (X = Cl, Br, I). Silver(I) halide and dpmp give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 is a dimer and has been observed for [(dpmp)Ag({mu}-X){sub 2}Ag(dpmp)] (X = Cl, Br or I). The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(dpmp){sub 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 is a dimer and has been observed for [(pdmp)Ag({mu}-X){sub 2}Ag(pdmp)] (X Cl, Br or I). The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(pdmp){sub 2}] (X = Cl, Br, I). Silver(I) halide and tmmp only give complexes with stoichiometry 1:1. 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 between silver and phosphorous atoms in the complexes obtained, it can be concluded that bulky ligands tend to give complexes with lower range of stoichiometry. In addition, the bulkier the ligand the longer the bond length between the silver and phosphorous atoms.« less

Authors:
 [1];  [2]
  1. Jurusan Kimia, FMIPA Universitas Negeri Malang, Jl. Surabaya 6 Malang 65145 (Indonesia)
  2. Chemistry, School of Biomedical, Biomolecular, and Chemical Sciences, The University of Western Australia, 35 Stirling Highway, Crawley WA 6009 (Australia)
Publication Date:
OSTI Identifier:
21136863
Resource Type:
Journal Article
Journal Name:
AIP Conference Proceedings
Additional Journal Information:
Journal Volume: 989; Journal Issue: 1; Conference: International conference on neutron and X-ray scattering 2007, Serpong and Bandung (Indonesia), 23-31 Jul 2007; Other Information: DOI: 10.1063/1.2906094; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0094-243X
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; BOND LENGTHS; CRYSTAL STRUCTURE; DIMERS; LIGANDS; MONOMERS; NEUTRON DIFFRACTION; ORGANIC PHOSPHORUS COMPOUNDS; PHOSPHINES; PYRIDINE; SILVER BROMIDES; SILVER COMPLEXES; SILVER IODIDES; STOICHIOMETRY; SYNTHESIS; X RADIATION

Citation Formats

Effendy, and White, A. H. Synthesis and X-ray Structural Study on the Complexes of Silver(I) Halide with Tricyclohexylephosphine, Diphenyl-(2,4,6-trimethoxy)phenylphosphine, Phenyl-2,4,6-trimethoxyphenyl phosphine, and Tris(2,4,6-trimethoxy)phenylphosphine. United States: N. p., 2008. Web. doi:10.1063/1.2906094.
Effendy, & White, A. H. Synthesis and X-ray Structural Study on the Complexes of Silver(I) Halide with Tricyclohexylephosphine, Diphenyl-(2,4,6-trimethoxy)phenylphosphine, Phenyl-2,4,6-trimethoxyphenyl phosphine, and Tris(2,4,6-trimethoxy)phenylphosphine. United States. doi:10.1063/1.2906094.
Effendy, and White, A. H. Mon . "Synthesis and X-ray Structural Study on the Complexes of Silver(I) Halide with Tricyclohexylephosphine, Diphenyl-(2,4,6-trimethoxy)phenylphosphine, Phenyl-2,4,6-trimethoxyphenyl phosphine, and Tris(2,4,6-trimethoxy)phenylphosphine". United States. doi:10.1063/1.2906094.
@article{osti_21136863,
title = {Synthesis and X-ray Structural Study on the Complexes of Silver(I) Halide with Tricyclohexylephosphine, Diphenyl-(2,4,6-trimethoxy)phenylphosphine, Phenyl-2,4,6-trimethoxyphenyl phosphine, and Tris(2,4,6-trimethoxy)phenylphosphine},
author = {Effendy and White, A. H.},
abstractNote = {A diverse array of structures for the complexes of silver(I) halide with triphenylphosphine (PPh{sub 3}) has been studied. The complexes may be described as being of the type [AgX(PPh{sub 3}){sub n}] (X = Cl, Br or I). The value of n varies in the range of 1-3. This also indicates that the stoichiometry of the complexes is in the range of 1-3. The complex with stoichiometry 1:1 is a tetramer. There are two structural types of tetramer reported, termed cubane and step or chair. The cubane structure has been reported for [AgX(PPh{sub 3})]{sub 4} (X = Cl, Br or I), while the step structure has only been reported for [AgI(PPh{sub 3})]{sub 4}. The complex with stoichiometry 1:2 may be a monomer or a dimer. The monomer has a quasi trigonal planar structural type and has only been reported for [AgBr(PPh{sub 3}){sub 2}]. The dimer has been reported for [(PPh{sub 3}){sub 2}Ag({mu}-X){sub 2}Ag(PPh{sub 3}){sub 2}] (X = Cl or Br) with silver atom in the distorted tetrahedral environment. The complex with stoichiometry 1:3 has a distorted tetrahedral structural type and has been reported for [AgX(PPh{sub 3}){sub 3}] (X = Cl, Br or I). Changing PPh{sub 3} with more hindered ligand such as tricyclohexylephosphine (Pcy{sub 3}) or derivative of PPh{sub 3} such as diphenyl-2,4,6-trimethoxy(phenyl)phosphine (dpmp), phenyl-bis{l_brace}2,4,6-trimethoxy(phenyl){r_brace} phosphine (pdmp), or tris{l_brace}2,4,6-trimethoxy(phenyl){r_brace}phosphine (tmpp) may give complexes with various structural types but with lower range of stoichiometry. Synthesis and X-ray structural study of these complexes has been done with the results summarized below. Silver(I) halide and Pcy{sub 3} give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 is a dimer or cubane. The dimer is observed for [(Pcy{sub 3})Ag({mu}-X){sub 2}Ag(Pcy{sub 3})] (X = Cl or Br). The unusual dimer is observed for [(Pcy{sub 3})Ag({mu}-I){sub 2}({mu}-py)Ag(Pcy{sub 3})] where the pyridine ligand is bonded to two silver atoms. The cubane is observed for [AgI(Pcy{sub 3})]{sub 4}. The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(Pcy{sub 3}){sub 2}] (X = Cl, Br, I). Silver(I) halide and dpmp give complexes with stoichiometry 1:1 and 1:2. The complex with stoichiometry 1:1 is a dimer and has been observed for [(dpmp)Ag({mu}-X){sub 2}Ag(dpmp)] (X = Cl, Br or I). The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(dpmp){sub 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 is a dimer and has been observed for [(pdmp)Ag({mu}-X){sub 2}Ag(pdmp)] (X Cl, Br or I). The complex with stoichiometry 1:2 has a quasi trigonal planar structural type and has been observed for [AgX(pdmp){sub 2}] (X = Cl, Br, I). Silver(I) halide and tmmp only give complexes with stoichiometry 1:1. 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 between silver and phosphorous atoms in the complexes obtained, it can be concluded that bulky ligands tend to give complexes with lower range of stoichiometry. In addition, the bulkier the ligand the longer the bond length between the silver and phosphorous atoms.},
doi = {10.1063/1.2906094},
journal = {AIP Conference Proceedings},
issn = {0094-243X},
number = 1,
volume = 989,
place = {United States},
year = {2008},
month = {3}
}