Crystal Structures and Vibrational and Solution and Solid-State (CPMAS) NMR Spectroscopic Studies in Triphenyl Phosphine, Arsine, and Stibine Silver(I) Bromate Systems, (R3E)xAgBrO3 (E = P, As, Sb; x = 1-4)

Adducts of triphenyl phosphine, triphenyl arsine, and triphenyl stibine with silver(I) bromate have been synthesized and characterized both in solution (1H and ESI MS spectroscopy) and in the solid state (IR, single-crystal X-ray structure analysis). The triphenyl phosphine complexes have been also investigated by 31P{1H} solution and 31P cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy. The topology of the structures in the solid state was found to depend on the nature of EPh3 and on the stoichiometric ratio AgBrO3/EPh3. In AgBrO3/PPh3 (1:1)4 (1) and AgBrO3/PPh3 (1:2) (2), the bromate is in the unfamiliar and hitherto structurally uncharacterized role of coordinating ligand, the complex having a mononuclear form in 2 and a less familiar tetrameric form in 1. In AgBrO3/AsPh3 (1:4)·CH3OH (7) and AgBrO3/SbPh3 (1:4)·C2H5OH (11), the cations are the familiar homoleptic [Ag(EPh3)4]+ array with the bromate role simply that of counterion. The AgBrO3/AsPh3 (1:2)2·0.7“H2O” derivative (6) is binuclear L2Ag(μ-BrO3)2AgL2 with a four-membered ring core (L = AsPh3).