Crystal Structures and Vibrational and Solution and Solid-State (CPMAS) NMR Spectroscopic Studies in Triphenyl Phosphine, Arsine, and Stibine Silver(I) Bromate Systems, (R₃E)<i>_x</i>AgBrO₃ (E = P, As, Sb; <i>x</i> = 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).本研究合成了三苯基膦（triphenyl phosphine）、三苯基胂（triphenyl arsine）与三苯基锑（triphenyl stibine）分别与溴酸银(I)（silver(I) bromate）形成的加合物，并分别在溶液相（采用¹H核磁共振波谱与电喷雾电离质谱（ESI MS））及固相（采用红外光谱（IR）、单晶X射线结构分析）对其完成表征。针对三苯基膦配合物，还通过溶液相³¹P{¹H}核磁共振波谱与³¹P交叉极化魔角旋转（CPMAS）核磁共振波谱开展了进一步研究。研究发现，固相结构的拓扑性质取决于EPh3的种类以及AgBrO3与EPh3的化学计量比。在AgBrO3与PPh3按1:1摩尔比形成的四聚体（化合物1）以及按1:2摩尔比形成的配合物（化合物2）体系中，溴酸根以一种前所未见、且迄今尚无结构表征的配位配体身份参与配位：化合物2为单核配合物，化合物1则为较为罕见的四聚体配合物。在AgBrO3/AsPh3（1:4）·CH₃OH（化合物7）与AgBrO3/SbPh3（1:4）·C₂H₅OH（化合物11）体系中，阳离子为经典的同配[Ag(EPh3)4]+结构，溴酸根仅充当抗衡离子。AgBrO3与AsPh3按1:2摩尔比形成的含0.7个结晶水的衍生物（化合物6）为双核配合物L2Ag(μ-BrO3)2AgL2，其核心为四元环结构（其中L=AsPh3）。