Klonowski Peter, Goloboy James C, Uribe-Romo Fernando J, Sun Furong, Zhu Lingyang, Gándara Felipe, Wills Corinne, Errington R John, Yaghi Omar M, Klemperer Walter G
Department of Chemistry, University of California , 419 Latimer Hall, Berkeley, California 94720, United States.
Inorg Chem. 2014 Dec 15;53(24):13239-46. doi: 10.1021/ic502617k. Epub 2014 Nov 19.
Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)6 to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O40(4-) (1) and SiW12O40(4-) (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The α-H2SiPtW11O40(4-) was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, (195)Pt NMR spectroscopy, (183)W NMR spectroscopy, and (183)W-(183)W 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anion salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.
将K8SiW11O39和K2Pt(OH)6的水溶液酸化至pH 4，然后加入过量的四甲基氯化铵（TMA），得到H2SiPtW11O40(4-)（1）和SiW12O40(4-)（2）的TMA盐的固体混合物。通过萃取到水溶液中将前者与后者分离，并将其转化为四正丁基铵（TBA）盐和钾盐TBA-1和K-1。使用元素分析、红外光谱、X射线晶体学、电喷雾电离质谱、(195)Pt核磁共振光谱、(183)W核磁共振光谱和(183)W-(183)W二维INADEQUATE核磁共振光谱，将α-H2SiPtW11O40(4-)鉴定为单取代的Keggin阴离子。TBA-1和K-1都很容易分别与其未取代的Keggin阴离子盐TBA-2和K-2共结晶，这就解释了历史上难以以纯形式分离某些铂取代杂多阴离子的原因。
