Spectroscopic and structural studies on 1:1 adducts of silver (I) salts with tricyclohexylphosphine

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Bowmaker, GA
Harvey, PJ
Healy, PC
Skelton, BW
White, AH
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The 1 : 1 adducts of silver(I) halides (AgX; X = Cl, Br or I) with tricyclohexylphosphine have been prepared and their room-temperature single-crystal structures, solid-state cross polarization magic angle spinning (CP MAS)31P NMR, solution 31P NMR and far-IR spectra determined. The solid-state structures of the chloride and bromide complexes recrystallized from pyridine are unsolvated, isomorphous, centrosymmetric dihalide-bridged dimers, [{AgX[P(C6H11)3]}2], with three-co-ordinate metal centres. Crystals are triclinic, space group P, a8.8, b9.4, c13.3 Ŭ 100, 92, 115஠Recrystallization of the iodide complex from pyridine (py) yielded a novel dimer consisting of [{AgI(py)0.5[P(C6H11)]3]}2] units in which the silver and phosphorus atoms are folded around the I I vector and towards a bridging pyridine ligand in a crevice co-ordination mode. Recrystallization of the iodide from substituted pyridine bases did not yield further examples of such complexes but rather crystals of an unsolvated cubane tetramer, [{AgI[P(C6H11)3]}4]. The far-IR spectra of the complexes exhibit bands due to v(AgX) vibrational modes at 225, 143 cm-1 for X = Cl, 189, 167, 135, 114 cm-1 for X = Br, 113, 83 cm-1 for X = I and at 115, 90 cm-1 for [{AgI(py)0.5[P(C6H11)3]}2]. These spectra are interpreted in terms of idealized C2h Ag(存)2Ag and Td Ag4I4 structures of the silver halide cores. The separation between the bands in the spectra of the dimeric species is a sensitive function of the extent of distortion of the cores from D2h symmetry. The solid-state CP MAS 31P NMR spectra of the dimers exhibit simple doublets with average 1J(P-Ag) coupling constants of 648 Hz for [{AgCl[P(C6H11)3]}2], 612 Hz for [{AgBr[P(C6H11)3]}2] and 552 Hz for [{AgI(py)0.5[P(C6H11)3]}2]. Solution 31P NMR spectra of the chloride and bromide complexes show well resolved sets of doublets due to 1J(P-107,109Ag) coupling at 25 and 0 àrespectively with average 1J(P-Ag) coupling constants of 642 and 627 Hz. The solution spectra of both the tetrameric and crevice iodide complexes are similar, showing broad signals at room temperature and doublets at -60 à[ 12, 1J(P-Ag)= 544 Hz]. These structural and spectroscopic results are compared with those for other 1 : 1 AgX : phosphine complexes.

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Journal of the Chemical Society. Dalton Transactions

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© 1996 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version.

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