Superacid Anions: Crystal and Molecular Structures of Oxonium Undecafluorodiantimonate(V), [H3O][Sb2F11], Cesium Fluorosulfate, CsSO3F, Cesium Hydrogen Bis(
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- 作者：Dingliang Zhang ; Steven J. Rettig ; James Trotter ; and Friedhelm Aubke
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：October 9, 1996
- 年：1996
- 卷：35
- 期：21
- 页码：6113 - 6130
- 全文大小：496K
- 年卷期：v.35,no.21(October 9, 1996)
- ISSN：1520-510X
文摘
In order to understand the reasons for the low nucleophilicity ofsuperacid anions, a systematic, comparativestudy of six superacid anions by single-crystal X-ray diffraction isundertaken. From magic acid,HSO3F-SbF5,surprisingly, single crystals of oxoniumundecafluorodiantimonate(V),[H3O][Sb2F11],1, are obtained. In theremaining five salts the cesium ion, Cs+, is used as thecountercation. Both CsSO3F, 2, and itssolvateCs[H(SO3F)2], 3, are derived fromthe Brönsted superacid HSO3F. The conjugatenoble metal superacid systemsHSO3F-Au(SO3F)3 andHSO3F-Pt(SO3F)4 providecesium tetrakis(fluorosulfato)aurate(III)Cs[Au(SO3F)4],4,and cesium hexakis(fluorosulfato)platinate(IV)Cs2[Pt(SO3F)6],5. Cesiumhexakis(fluorosulfato)antimonate(V)Cs[Sb(SO3F)6], 6, whosesynthesis is described here in detail, provides evidence for thepossible existence of anew conjugate superacid system,HSO3F-Sb(SO3F)5.Crystals of [H3O][Sb2F11](1, H3F11OSb2) areorthorhombic,a = 12.744(2) Å, b = 39.371(2) Å,c = 11.407(3) Å, Z = 24, and spacegroup Pbca; those of CsSO3F(2,CsFO3S) are monoclinic, a = 7.7243(6) Å,b = 8.1454(6) Å, c = 7.7839(7) Å,
= 110.832(7)
ntities/deg.gif">, Z = 4, andspace group P21/a; those ofCs[H(SO3F)2] (3,HCsF2O6S2) are monoclinic,a = 13.371(2) Å, b = 7.731(2) Å,c= 9.485(2) Å, = 128.375(7)ntities/deg.gif">, Z = 4,and space group C2/c; those ofCs[Au(SO3F)4] (4,AuCsF4O12S4) aremonoclinic, a = 17.725(2) Å, b =5.822(2) Å, c = 14.624(2) Å, =102.120(9)ntities/deg.gif">, Z = 4, and space groupC2/c;those of Cs2[Pt(SO3F)6](5,Cs2F6O18PtS6) aretrigonal, a = 9.070(1) Å, c =7.6028(7) Å, Z = 1, space groupP321; and those ofCs[Sb(SO3F)6] (6,CsF6O18S6Sb) are trigonal,a = 12.0317(7) Å, c = 12.026(2)Å, Z = 3,space group Rntities/thremacr.gif">. The structures were solved byPatterson (1, 2, and 6) or direct(4 and 5) methods (that of 3isa redetermination) and were refined by full-matrix least-squaresprocedures to R = 0.036, 0.029, 0.027, 0.030,0.048, and 0.039 (Rw = 0.032,0.027, 0.026, 0.029, 0.045, and 0.037) for 4110, 2321, 1362, 1671, 738,and 1485reflections with I ntities/ge.gif"> 3
(F2),for 1, 2, 3, 4,5, and 6, respectively. In additionCs[Sb(SO3F)6] is characterizedbyvibrational spectroscopy.
= 110.832(7)ntities/deg.gif">, Z = 4, andspace group P21/a; those ofCs[H(SO3F)2] (3,HCsF2O6S2) are monoclinic,a = 13.371(2) Å, b = 7.731(2) Å,c= 9.485(2) Å, = 128.375(7)ntities/deg.gif">, Z = 4,and space group C2/c; those ofCs[Au(SO3F)4] (4,AuCsF4O12S4) aremonoclinic, a = 17.725(2) Å, b =5.822(2) Å, c = 14.624(2) Å, =102.120(9)ntities/deg.gif">, Z = 4, and space groupC2/c;those of Cs2[Pt(SO3F)6](5,Cs2F6O18PtS6) aretrigonal, a = 9.070(1) Å, c =7.6028(7) Å, Z = 1, space groupP321; and those ofCs[Sb(SO3F)6] (6,CsF6O18S6Sb) are trigonal,a = 12.0317(7) Å, c = 12.026(2)Å, Z = 3,space group Rntities/thremacr.gif">. The structures were solved byPatterson (1, 2, and 6) or direct(4 and 5) methods (that of 3isa redetermination) and were refined by full-matrix least-squaresprocedures to R = 0.036, 0.029, 0.027, 0.030,0.048, and 0.039 (Rw = 0.032,0.027, 0.026, 0.029, 0.045, and 0.037) for 4110, 2321, 1362, 1671, 738,and 1485reflections with I ntities/ge.gif"> 3(F2),for 1, 2, 3, 4,5, and 6, respectively. In additionCs[Sb(SO3F)6] is characterizedbyvibrational spectroscopy.