Structual and solid state P N.M.R. studies of Tetrameric 1 : 1 Butyldiphenylphosphine Complexes of Silver(I) Halides
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Tetrameric 1:1 complexes of butyldiphenylphosphine (PPh2Bu) with silver halides AgX (X = Cl , Br and I) have been synthesized, and characterized in the solid state by single-crystal X-ray diffraction studies and solid-state 31P n.m.r. Crystals of [(PPh2Bu) AgCl ]4 and [(PPh2Bu) AgBr ]4 are isostructural, crystallizing in the tetragonal space group 14 with a 16.853(4), c 11.697(4) ? and R 0.060 for 999 'observed' reflections for X = Cl, and a 16.944(4), c 11.893(9) ? and R 0.044 for 835 'observed' reflections for X = Br. The structures consist of 'cubane' units with core distances of Ag-P 2.365(8), Ag- Cl 2.712(7), 2.682(6) and 2.569(6) ? for the chloride, and Ag-P 2.408(6), Ag-Br 2.819(3), 2.806(3) and 2.670(3) ? for the bromide. Crystals of [(PPh2Bu) AgI ]4 crystallize in the same space group with similar cell dimensions, a 16.559(4) and c 12.819(3) ?, and R 0.053 for 638 'observed' reflections. However, the tetramers in this complex are rotated by 45ࠡround the c axis with apparent relaxation of strain at the Ag-P bond. The ligand conformation is such that the butyl groups are oriented along the c axis rather than lying in the ab plane as found for the chloride and bromide structures. The bond distances for the I3AgP core are Ag-P 2.43(1), Ag-I 2.928(4), 2.882(4) and 2.885(4) ?. The ligand substituents in this complex exhibit very high thermal motion although no disorder is resolved. Solid-state CPMAS 31P n.m.r. spectra of the chloride and bromide complexes each show a simple doublet with line spacing of 640 and 595 Hz respectively assignable to 1J(107,109Ag,31P) scalar coupling. The spectrum of the iodide complex, however, consists of a broad single peak suggestive of a high degree of disorder in the crystal lattice, consistent with the structural results.
Australian Journal of Chemistry