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

DOI: 10.1039/dt9960002459

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2459 - 2465 (1996)

Update date:2022-07-30

Topics:

Authors:

Bowmaker, Graham A.Bowmaker, Graham A.

EffendyEffendy

Harvey, Peta J.Harvey, Peta J.

Healy, Peter C.Healy, Peter C.

Skelton, Brian W.Skelton, Brian W.

White, Allan H.White, Allan H.

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Article abstract of DOI:10.1039/dt9960002459

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 P1, a ≈ 8.8, b ≈ 9.4, c ≈ 13.3 A, α ≈ 100, β ≈ 92, γ ≈ 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' coordination 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(μ-X)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°C respectively 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°C [δ 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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