Journal of the Chemical Society, Dalton Transactions p. 2449 - 2457 (1996)
Update date:2022-08-04
Topics:
Bowmaker, Graham A.
Effendy
Harvey, Peta J.
Healy, Peter C.
Skelton, Brian W.
White, Allan H.
A series of monomeric [AgX{P(C6H11)3}2] complexes have been prepared for X = CN, I, Br, Cl, SCN, NCO, NO3 or ClO4 and characterized by single-crystal X-ray determinations, solid-state cross polarization magic angle spinning (CP MAS) 31P NMR, solution 31P NMR and far-infrared spectroscopy. For X = CN, I, Br, Cl or SCN the crystal structures are isomorphous, crystallizing in a monoclinic C2/c cell with a ≈ 17, b ≈ 9.3, c ≈ 25 A, β ≈ 110°, Z = 4; the SCN complex exhibits anion disorder/space group ambiguity. For X = NCO or NO3 (redetermined) the structures are isomorphous with the previously studied perchlorate, crystallizing in a triclinic P1 cell derivative of the C2/c array with a ≈ 9.3, b ≈ 9.8, c ≈ 23 A, α ≈ 95, β ≈ 96, γ≈ 116°. The Ag-P bond lengths correlate inversely with the P-Ag-P angles and depend on the donor properties of the anion X, with, however, a reverse trend noted for the halide complexes. The solid-state CP MAS 31P NMR spectra show splitting due to 1J(P-Ag) coupling which progressively increases from 322 Hz for X = CN to 505 Hz for X = ClO4. For the triclinic species further splitting is observed and assigned to 2J(P-P) coupling between the crystallographically inequivalent phosphorus atoms. These NMR results are consistent with the structural results except for the chloride and perchlorate systems where experiments suggest that both triclinic and monoclinic phases co-crystallize in proportions which depend on the recrystallization procedures. Solution 31P NMR spectra show doublets assignable to 1:2 species. For X = Br, Cl, NCO or SCN signals assignable to 1:1 species are also observed. Comparison with solid-state data show differences in 1J(P-Ag) that are ascribed to differences in 0(P-Ag-P) in the solution and solid states. Far-IR spectra of the halide and pseudo-halide complexes in the series exhibit single bands due to v(AgX) vibrational modes at 207, 149, 121 for X = Cl, Br or I and at 288, 241 and 174 cm-1 for X = CN, NCO or SCN, these latter results providing fare data for the vibrational frequencies of terminal Ag-C, Ag-N and Ag-S bonds.
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