Diphosphines as bridging ligands in polymeric and dimeric thione-S-ligated Ag(I) nitrate complexes |
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| Authors: | P Aslanidis P.J Cox P Karagiannidis |
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| Affiliation: | a Inorganic Chemistry Laboratory, Faculty of Chemistry, Aristotle University of Thessaloniki, P.O. Box 135, GR- 541 24 Thessaloniki, Greece
b School of Pharmacy, The Robert Gordon University, Schoolhill, Aberdeen AB 10 1FR, Scotland, UK |
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| Abstract: | Reactions of silver(I) nitrate with equimolar amounts of the diphos ligands 1,4-bis(diphenylphosphino)butane (dppb) or 1,2-bis(diphenylphosphino)ethane (dppe) and some heterocyclic thiones (L) in acetonitrile/methanol solvent afforded mixed-ligand complexes, the nature of which was found to be strongly influenced by the backbone length of the diphosphine ligand. The longer chained diphos ligand formed a series of dinuclear complexes of the type [Ag(dppb)(L)]2(NO3)2 with both the diphosphine and thione ligands acting as bridging ligands between the two four-coordinate pseudo-tetrahedrally coordinated metal centers. In the unique case of L=4-methyl-5-trifluoromethyl-4H-1,2,4-triazoline-3(2H)-thione (mftztH), the reaction proceeded under exclusion of the thione ligand from the coordination sphere and coordination of the nitrate anions instead, leading to the diphosphine-doubly bridged dimeric compound [Ag(dppb)(NO3)]2. On the other hand, the complexes produced when using the short bite 1,2-bis(diphenylphosphino)ethane (dppe) turned out to be diphosphine-bridged cationic polymers of the type [Ag(dppe)(L)2]n(NO3)n. The structures of one representative for each of the two aforementioned series of complex compounds, namely [Ag(dppb)(py2SH)]2(NO3)2 · 2H2O and [Ag(dppe)(pymtH)2]n(NO3)n, have been established by single-crystal X-ray diffraction. |
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| Keywords: | Silver(I) complexes Heterocyclic thiones 1,2-bis(diphenylphosphino)ethane 1,4-bis(diphenylphosphino)butane Crystal structures |
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