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氟磺酸鹽

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氟磺酸鹽
英文名 Fluorosulfate
識別
CAS號 15181-47-2  checkY
性質
化學式 SO3F
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。

氟磺酸鹽氟磺酸的鹽,含有SO3F離子。氟磺酸根可以看作是硫酸氫根的一個羥基被氟取代而成的離子。[1]氟磺酸根離子與金屬陽離子形成配合物的傾向較低。由於氟的大小和氧相似,氟磺酸根基本是四面體形的,類似於高氯酸根。它和硫酸氫根 HSO
4
等電子體[2] 如果氟磺酸的氫原子被替換成有機基團,就會形成氟磺酸酯英語Fluorosulfonate

在溶液中,氟磺酸根會完全電離。這個離子的體積為 47.8 cm3/mol。[3]大部分金屬和季銨鹽都可以形成氟磺酸鹽。[3]氟磺酸鹽可以由金屬氯化物和無水氟磺酸反應而成,並放出氯化氫。複分解反應製備法包括金屬硫酸鹽和氟磺酸鋇的反應,或是金屬氯化物和氟磺酸銀的反應,會留下沉澱。[3]

氟磺酸根的配位性很弱,且難以氧化。它在歷史上作為很重要的非配位陰離子模型。然而,到了21世紀,氟硫酸鹽在這種用途中被BARF英語Tetrakis(3,5-bis(trifluoromethyl)phenyl)borate取代了。[2]

很多二元氟磺酸鹽是已知的。非金屬氟磺酸鹽包括鹵素和氙的氟磺酸鹽。[2]一些三元氟磺酸鹽也是已知的,包括 Cs[Sb(SO3F)6]、Cs[Au(SO3F)4]和 Cs2[Pt(SO3F)6][2]

相關的離子化合物有氟代硒酸鹽 SeO3F氟代亞硫酸鹽 SO2F[4]氟化硫酸鹽英語sulfate fluorides則是另外一類化合物,它們的氟離子沒有和硫酸根連接。

reederite-(Y)英語reederite-(Y)是一種含有氟磺酸根的天然礦物。它是一種混合陰離子化合物英語mixed anion compound,其中也存在著碳酸根和氯離子。[5]

化合物列表

[編輯]
化學式 名稱 顏色 分解溫度(°C) 分解產物 晶體結構 參考資料
LiSO3F 氟磺酸鋰 C2/m a=8.54 b=7.62 c=4.98 β=90.0 V=81 [1]
Be(SO3F)2 氟磺酸鈹 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 氟磺酸銨 正交晶系

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

[1]
N(CH3)4SO3F 四甲基氟磺酸銨 正交晶系

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

[1]
NOSO3F 氟磺酸亞硝醯 熔點 156 密度 1.96 [4][7]
NO2SO3F 氟磺酸硝醯 [7]
S2O6F2 過氧化氟磺醯 [2]
NaSO3F 氟磺酸鈉 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 氟磺酸鎂 SO3 [4]
Al(SO3F)2.3CH3CN [8]
Al(SO3F)3 氟磺酸鋁 白色 聚合物,氟磺酸根是二齒橋接配體 [9]
Si(SO3F)4 氟磺酸矽 S2O5F2
SiO2
[4]
PO(SO3F)3 氟磺酸磷(V)醯 S2O5F2 [4]
PO(SO3F) 氟磺酸磷(III)醯 [6]
ClSO3F 氟磺酸氯 [2]
ClO2SO3F 氟磺酸氯醯 紅或淺黃 低熔點 [10]
KSO3F 氟磺酸鉀 Pnma a=8.62 b=5.84 c=7.35 V=92.5 [1]
Ca(SO3F)2 氟磺酸鈣 CaF2 SO3 [6]
Ti(SO3F)4 氟磺酸鈦 S2O5F2 [4]
VO(SO3F)3 氟磺酸氧釩 深紅色液體
CrO2(SO3F)2 氟磺酸氧鉻 綠或棕 [11]
Mn(SO3F)2 氟磺酸錳(II) [6]
MnO(SO3F) 氟磺酸氧錳(III) 深棕 [6]
Mn(SO3F)3 氟磺酸錳(III) [12]
Mn(CO)4(SO3F) 四羰基氟磺酸錳 [12]
Mn(CO)5(SO3F) 五羰基氟磺酸錳 [12]
Rb2Mn(SO3F)5 [12]
Cs2Mn(SO3F)5 [12]
Fe(SO3F)3 氟磺酸鐵 灰綠色 230 S2O5F2
SO3
FeF3
[13]
CoO(SO3F) 氟磺酸氧鉻 巧克力色 [6]
Ni(SO3F)2 氟磺酸鎳 [6]
Ni(py)4(SO3F)2

py=吡啶

[14]
NiO(SO3F) 氟磺酸氧鎳 深灰色 [6]
Cu(SO3F)2 氟磺酸銅 淺黃或白 210 S2O5F2
SO3
CuSO4
CuF2
[13]
Cu(py)4(SO3F)2 py=pyridine [14]
Cu(SO3F).CH3CN [8]
Zn(SO3F)2 氟磺酸鋅 白色 280 SO3
ZnF2
[13]
Zn(py)4(SO3F)2 py=pyridine [14]
Ga(SO3F)3 氟磺酸鎵 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 紅色液體 [2]
RbSO3F 氟磺酸銣 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 氟磺酸鍶 SO2F2 [6]
MoO2(SO3F)2 [17]
Nb(SO3F)5 氟磺酸鈮 無色溶液 25 SO3 [18]
NbO(SO3F)3 氟磺酸氧鈮 黃色液體 [17]
Ru(SO3F)3 氟磺酸釕 非常深的紅 [19]
CsRu(SO3F)4 深棕色 [19]
ClO2Ru(SO3F)4 黑色 [19]
CsRu(SO3F)5 紅棕色 [19]
Cs2Ru(SO3F)6 亮橙色 [19]
K2Ru(SO3F)6 亮橙色 [19]
Rh(SO3F)3 氟磺酸銠 亮橙色 190 [20]
Pd(SO3F)2 氟磺酸鈀(II) 紫色 250 SO3 PdF2 [21]
Pd(SO3F)3 氟磺酸鈀(III) 深棕色 180 [21]
Pd(CO)2(SO3F)2 黃色 [22]
c-Pd2(μ-CO)2](SO3F)2 橙色 單斜晶系

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

[23]
AgSO3F 氟磺酸銀(I) P21/m a=5.413 b=8.174 c=7.544 β=94.60 V=83.17 Z=4 [1]
Ag(SO3F)2 氟磺酸銀(II) 深棕色 室溫
>120時反應迅速
Ag3(SO3F)4
SO3F
單斜晶系

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 氟磺酸銀(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 單斜晶系

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 氟磺酸鎘 [6]
In(SO3F)3 氟磺酸銦 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)合銻(V)酸銫 三方晶系

Ra = 12.0317 Å, c = 12.026 Å, Z = 3

[27]
TeF5SO3F [6]
ISO3F 氟磺酸碘 [28]
ICl2SO3F [28]
IBr2SO3F 鏽棕色 90 ISO3F, Br2 [28]
IO2SO3F 氟磺酸碘醯 黃色 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 氟磺酸銫 l41/a a=5.611 b=5.611 c=14.13 V=111.3 Z=4 [1]
Cs[H(SO3F)2] 氟磺酸氫銫 [27]
Ba(SO3F)2 氟磺酸鋇 BaSO4 SO2F2 [6]
Ho(SO3F)3 氟磺酸鈥 [30]
Ta(SO3F)5 氟磺酸鉭 無色溶液 [18]
TaO(SO3F)3 氟磺酸氧鉭 黃色液體 [17]
WO(SO3F)4 四(氟磺酸根)氧鎢 無色液體 [17][31]
ReO2(SO3F)3 三(氟磺酸根)二氧錸 白色固體 [17]
ReO3(SO3F) 氟磺酸三氧錸 黃色液體 [17]
Re(CO)5(SO3F) [12]
Os(SO3F)3 亮綠色 130 [20]
Ir(SO3F)3 氟磺酸銥(III) [32]
Ir(SO3F)4 氟磺酸銥(IV) [33]
Cs2Ir(SO3F)6 [33]
BaIr(SO3F)6 [33]
(ClO2)2Ir(SO3F)6 [33]
mer-Ir(CO)3(SO3F)3 無色 單斜晶系

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

[32]
Pt(SO3F)4 氟磺酸鉑 [22]
Cs2[Pt(SO3F)6] 六(氟磺酸根)合鉑(IV)酸銫 [27]
Pt(CO)2(SO3F)2 奶油色 [22]
AuICO(SO3F) [22]
AuII(SO3F)2 氟磺酸金(II) 黃紅色 [34]
AuIII(SO3F)3 氟磺酸金(III) [22]
Cs[Au(SO3F)4] 四(氟磺酸根)合金(III)酸銫 單斜晶系

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 氟磺酸鉈(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) 氟磺酸氧鉈(III) 棕色 [6]
Tl(SO3F)3 氟磺酸鉈(III) [26]
Pb(SO3F)4 氟磺酸鉛(IV) [18][35]
Bi(SO3F)3 [18][36]
Th(SO3F)4 氟磺酸釷 [18]
U(SO3F)2 氟磺酸鈾(II) 黃色 [17]
U(SO3F)3 氟磺酸鈾(III) 綠色 [17]
U(SO3F)4 氟磺酸鈾(IV) 肉色 [18][37]
Na2U(SO3F)6 [17]
UO(SO3F)2 氟磺酸鈾(IV)醯 [37]
UO2(SO3F)2 氟磺酸鈾(VI)醯 [37]

參考資料

[編輯]
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