氟磺酸盐

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氟磺酸盐
英文名 Fluorosulfate
识别
CAS号 15181-47-2  checkY
性质
化学式 SO3F−
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

氟磺酸盐是氟磺酸的盐，含有SO3F−离子。氟磺酸根可以看作是硫酸氢根的一个羟基被氟取代而成的离子。[1]氟磺酸根离子与金属阳离子形成配合物的倾向较低。由于氟的大小和氧相似，氟磺酸根基本是四面体形的，类似于高氯酸根。它和硫酸氢根 HSO−
4是等电子体。[2] 如果氟磺酸的氢原子被替换成有机基团，就会形成氟磺酸酯（英语：Fluorosulfonate）。

在溶液中，氟磺酸根会完全电离。这个离子的体积为 47.8 cm3/mol。[3]大部分金属和季铵盐都可以形成氟磺酸盐。[3]氟磺酸盐可以由金属氯化物和无水氟磺酸反应而成，并放出氯化氢。复分解反应制备法包括金属硫酸盐和氟磺酸钡的反应，或是金属氯化物和氟磺酸银的反应，会留下沉淀。[3]

氟磺酸根的配位性很弱，且难以氧化。它在历史上作为很重要的非配位阴离子模型。然而，到了21世纪，氟硫酸盐在这种用途中被BARF（英语：Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate）取代了。[2]

很多二元氟磺酸盐是已知的。非金属氟磺酸盐包括卤素和氙的氟磺酸盐。[2]一些三元氟磺酸盐也是已知的，包括 Cs[Sb(SO3F)6]、Cs[Au(SO3F)4]和 Cs2[Pt(SO3F)6][2]。

相关的离子化合物有氟代硒酸盐 SeO3F− 和氟代亚硫酸盐 SO2F−。[4]氟化硫酸盐（英语：sulfate fluorides）则是另外一类化合物，它们的氟离子没有和硫酸根连接。

reederite-(Y)（英语：reederite-(Y)）是一种含有氟磺酸根的天然矿物。它是一种混合阴离子化合物（英语：mixed anion compound），其中也存在着碳酸根和氯离子。[5]

化合物列表

化学式 名称 颜色 分解温度（°C） 分解产物 晶体结构 参考资料
LiSO3F 氟磺酸锂 C2/m a=8.54 b=7.62 c=4.98 β=90.0 V=81 [1]
Be(SO3F)2 氟磺酸铍 SO3 [6]
CF3(SO3F) 氟磺酸三氟甲酯 [6]
CF2(SO3F)2 [6]
CF(SO3F)3 [6]
C(SO3F)4 氟磺酸碳 [6]
NH4SO3F 氟磺酸铵 正交晶系

Pnma a=8.97 b=6.00 c=7.54 V=101.4 Z=4

[1]
N(CH3)4SO3F 四甲基氟磺酸铵 正交晶系

Pnma a=8.38 b=8.38 c=5.86 V=102.88 Z=4

[1]
NOSO3F 氟磺酸亚硝酰 熔点 156 密度 1.96 [4][7]
NO2SO3F 氟磺酸硝酰 [7]
S2O6F2 过氧化氟磺酰 [2]
NaSO3F 氟磺酸钠 六方晶系

a=5.4812 b=5.4812 c=6.5172 V=169.57 Z=2

密度 2.390

[1]
Mg(SO3F)2 氟磺酸镁 SO3 [4]
Al(SO3F)2.3CH3CN [8]
Al(SO3F)3 氟磺酸铝 白色 聚合物，氟磺酸根是二齿桥接配体 [9]
Si(SO3F)4 氟磺酸硅 S2O5F2
SiO2 		[4]
PO(SO3F)3 氟磺酸磷(V)酰 S2O5F2 [4]
PO(SO3F) 氟磺酸磷(III)酰 [6]
ClSO3F 氟磺酸氯 [2]
ClO2SO3F 氟磺酸氯酰 红或浅黄 低熔点 [10]
KSO3F 氟磺酸钾 Pnma a=8.62 b=5.84 c=7.35 V=92.5 [1]
Ca(SO3F)2 氟磺酸钙 CaF2 SO3 [6]
Ti(SO3F)4 氟磺酸钛 S2O5F2 [4]
VO(SO3F)3 氟磺酸氧钒 深红色液体
CrO2(SO3F)2 氟磺酸氧铬 绿或棕 [11]
Mn(SO3F)2 氟磺酸锰(II) [6]
MnO(SO3F) 氟磺酸氧锰(III) 深棕 [6]
Mn(SO3F)3 氟磺酸锰(III) [12]
Mn(CO)4(SO3F) 四羰基氟磺酸锰 [12]
Mn(CO)5(SO3F) 五羰基氟磺酸锰 [12]
Rb2Mn(SO3F)5 [12]
Cs2Mn(SO3F)5 [12]
Fe(SO3F)3 氟磺酸铁 灰绿色 230 S2O5F2
SO3
FeF3 		[13]
CoO(SO3F) 氟磺酸氧铬 巧克力色 [6]
Ni(SO3F)2 氟磺酸镍 [6]
Ni(py)4(SO3F)2

py=吡啶

[14]
NiO(SO3F) 氟磺酸氧镍 深灰色 [6]
Cu(SO3F)2 氟磺酸铜 浅黄或白 210 S2O5F2
SO3
CuSO4
CuF2 		[13]
Cu(py)4(SO3F)2 py=pyridine [14]
Cu(SO3F).CH3CN [8]
Zn(SO3F)2 氟磺酸锌 白色 280 SO3
ZnF2 		[13]
Zn(py)4(SO3F)2 py=pyridine [14]
Ga(SO3F)3 氟磺酸镓 白色 240 SO3 聚合物 [15][16]
As(SO3F)3 氟磺酸砷 S2O5F2 [4]
AsF2(SO3F)3 [6]
AsF3(SO3F)2 [6]
BrSO3F 氟磺酸溴 红色液体 [2]
RbSO3F 氟磺酸铷 正交晶系

Pnma a=8.7812 b=6.0318 c=7.5108 V=397.82 Z=4

密度 3.081

[1]
Sr(SO3F)2 氟磺酸锶 SO2F2 [6]
MoO2(SO3F)2 [17]
Nb(SO3F)5 氟磺酸铌 无色溶液 25 SO3 [18]
NbO(SO3F)3 氟磺酸氧铌 黄色液体 [17]
Ru(SO3F)3 氟磺酸钌 非常深的红 [19]
CsRu(SO3F)4 深棕色 [19]
ClO2Ru(SO3F)4 黑色 [19]
CsRu(SO3F)5 红棕色 [19]
Cs2Ru(SO3F)6 亮橙色 [19]
K2Ru(SO3F)6 亮橙色 [19]
Rh(SO3F)3 氟磺酸铑 亮橙色 190 [20]
Pd(SO3F)2 氟磺酸钯(II) 紫色 250 SO3 PdF2 [21]
Pd(SO3F)3 氟磺酸钯(III) 深棕色 180 [21]
Pd(CO)2(SO3F)2 黄色 [22]
c-Pd2(μ-CO)2](SO3F)2 橙色 单斜晶系

C2/c a=11.495 b=8.255 c=9.556 β =91.94 Z=8

[23]
AgSO3F 氟磺酸银(I) P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4 [1]
Ag(SO3F)2 氟磺酸银(II) 深棕色 室温
>120时反应迅速 		Ag3(SO3F)4
SO3F• 		单斜晶系

a=10.5130 Å, b= 7.7524 Å, c = 8.9366 Å, β = 117.867° V =643.88 Å3, Z = 4

密度 3.15 gcm−3

[24]
Ag2O(SO3F)2 黑色 [6]
AgI2AgII(SO3F)4 氟磺酸银(I,II) 黑色 [24]
KAgI2AgII(SO3F)5 正交晶系

P 2221, a = 6.4736 b = 7.3915 c = 17.7736

[25]
RbAgI2AgII(SO3F)5 正交晶系

P 2221, a = 6.4828 b = 7.3551c = 18.0262

[25]
RbAg(SO3F)3 单斜晶系

P 21/m , a = 15.815 b = 15.486 c = 17.021 β = 101.513

[25]
CsAg(SO3F)3 三斜晶系

P1_ , a = 14.9241 b = 9.7046 c = 17.8465 α = 109.116°, β = 84.655° γ = 119.171°

[25]
Cd(SO3F)2 氟磺酸镉 [6]
In(SO3F)3 氟磺酸铟 聚合物 [26]
Sn(SO3F)4 S2O5F2 [4]
SbF4SO3F [6]
Sb(SO3F)2.2CH3CN [8]
Cs[Sb(SO3F)6] 六(氟磺酸根)合锑(V)酸铯 三方晶系

R3̄ a = 12.0317 Å, c = 12.026 Å, Z = 3

[27]
TeF5SO3F [6]
ISO3F 氟磺酸碘 [28]
ICl2SO3F [28]
IBr2SO3F 锈棕色 90 ISO3F, Br2 [28]
IO2SO3F 氟磺酸碘酰 黄色 100 [29]
IF3(SO3F)2 二(氟磺酸根)三氟化碘 [4]
FXe(SO3F) [6]
Xe(SO3F)2 氟磺酸氙(II) [2]
F5Xe(SO3F) 氟磺酸五氟化氙 [6]
CsSO3F 氟磺酸铯 l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4 [1]
Cs[H(SO3F)2] 氟磺酸氢铯 [27]
Ba(SO3F)2 氟磺酸钡 BaSO4 SO2F2 [6]
Ho(SO3F)3 氟磺酸钬 [30]
Ta(SO3F)5 氟磺酸钽 无色溶液 [18]
TaO(SO3F)3 氟磺酸氧钽 黄色液体 [17]
WO(SO3F)4 四(氟磺酸根)氧钨 无色液体 [17][31]
ReO2(SO3F)3 三(氟磺酸根)二氧铼 白色固体 [17]
ReO3(SO3F) 氟磺酸三氧铼 黄色液体 [17]
Re(CO)5(SO3F) [12]
Os(SO3F)3 亮绿色 130 [20]
Ir(SO3F)3 氟磺酸铱(III) [32]
Ir(SO3F)4 氟磺酸铱(IV) [33]
Cs2Ir(SO3F)6 [33]
BaIr(SO3F)6 [33]
(ClO2)2Ir(SO3F)6 [33]
mer-Ir(CO)3(SO3F)3 无色 单斜晶系

P21/c, Z = 4, a = 8.476 b = 12.868 c = 12.588 β = 108.24°, V = 1304.0

[32]
Pt(SO3F)4 氟磺酸铂 [22]
Cs2[Pt(SO3F)6] 六(氟磺酸根)合铂(IV)酸铯 [27]
Pt(CO)2(SO3F)2 奶油色 [22]
AuICO(SO3F) [22]
AuII(SO3F)2 氟磺酸金(II) 黄红色 [34]
AuIII(SO3F)3 氟磺酸金(III) [22]
Cs[Au(SO3F)4] 四(氟磺酸根)合金(III)酸铯 单斜晶系

C2/c a = 17.725 Å, b = 5.822 Å, c = 14.624 Å, β = 102.120°, Z = 4

[27]
Hg(SO3F)2 氟磺酸汞 密度 3.715 [13]
TlSO3F 氟磺酸铊(I) 正交晶系

a=5.2205 b=5.5141 c=13.4378 V=386.83 Z=4

密度 5.210

[1]
TlO(SO3F) 氟磺酸氧铊(III) 棕色 [6]
Tl(SO3F)3 氟磺酸铊(III) [26]
Pb(SO3F)4 氟磺酸铅(IV) [18][35]
Bi(SO3F)3 [18][36]
Th(SO3F)4 氟磺酸钍 [18]
U(SO3F)2 氟磺酸铀(II) 黄色 [17]
U(SO3F)3 氟磺酸铀(III) 绿色 [17]
U(SO3F)4 氟磺酸铀(IV) 肉色 [18][37]
Na2U(SO3F)6 [17]
UO(SO3F)2 氟磺酸铀(IV)酰 [37]
UO2(SO3F)2 氟磺酸铀(VI)酰 [37]

参考资料

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  32. ^ 32.0 32.1 Wang, Changqing; Lewis, Andrew R.; Batchelor, Raymond J.; Einstein, Frederick W. B.; Willner, Helge; Aubke, Friedhelm. Synthesis, Molecular Structure, and Vibrational Spectra of mer -Tris(carbonyl)iridium(III) Fluorosulfate, mer -Ir(CO) 3 (SO 3 F) 3. Inorganic Chemistry. January 1996, 35 (5): 1279–1285. ISSN 0020-1669. PMID 11666319. doi:10.1021/ic9506769 （英语）. 
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  34. ^ Willner, H.; Mistry, F.; Hwang, G.; Herring, F.G.; Cader, M.S.R.; Aubke, F. Fluorosulfate derivatives of divalent gold. Journal of Fluorine Chemistry. April 1991, 52 (1): 13–27. doi:10.1016/S0022-1139(00)80318-8. 
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