SUPERACIDS

V. D. SHTEINGARTS

. .
The paper is an introduction into a new chapter of
chemistry which appeared due to the discovery
and exploration of the
structure and properties
of substances possessing
superhigh acidity. They
are promising for new
reactions to be found and
new approaches to be
developed in synthesis
and catalysis.
fl flflfl ,

fl
, fl
fl fl
.

, , , . .
- , .
.
, ,
(superacids).
-
[1].

Ka [1],

HY :
Y + H3O+,

HY + H2O

[ Y ] [ H3 O+ ]
K a = ----------------------------[ HY ]

.., 1999

pK a = lg K a ;

82

(1)
(2)

,
, . -
(1) . , , , ,
, .
(B)
(S) :
HY + B

Y + HB

(3)

HY

, 3, 1999

(B + S)
H0 [2]:
a H+ f B
C BH+
- = pK BH+ log ----------,
H 0 = log ------------f BH+
CB
pK BH+ = log K BH+ ;

(4)

a H+ a B a H+ f B C B
- = -------------- -----------,
K BH+ = ------------a BH+
f BH+ C BH+

, f ,
, a = fC.

,

,

C BH+ C B .

H0 , .
-, f B f BH+
, .
, (5)
:
+

Ar N

O
O

+ H+

Ar N

(5)

( 20 30 , 3- 2,4,6-)
, ,
. ,
, ,
, +. , ,
C BH+ C B .
-,
pK BH+ . (4) ,
(1), ,
f = 1, H0 = pH , , pK BH+ =
= pH + log( C BH+ C B ). - (B1) log ( C B1 H+ C B1 ) pK B1 H+
.

..

,
(B2) , C BH+ C B ,

C B1 H+
C B2 H+
- log -----------pK B1 H+ pK B2 H+ = log -----------C B1
C B2

(6)

pK BH+
. H0 .
H0
, ,
.
,
100%- , 0 = 12,
0 .
HClO4 ,
0=
= 13. (0= 13,8). ,
SO3 + HCl = HSO3Cl , SO3
Hl
.
( . ) HSO3F: 0 =
= 15,1. ( 89
163), , , ,
SO3 HF , .

CF3SO3H (0 = 14,1). , , HSO3F, .

(

) CH3SO3H.
,
, 0 = 16. ,
0 .
,
.

83

(.
[1]), H0 ,
, , .
:
, ,
.
- ,
,
, ,
:
A + HY:

HYA

(7)

HY,
( ), , HY, - ,
YA,
(8), ,
Y ,
HY (3). , , HYA,
HY,
HYA + B

YA + HB+

(8)

HY
, ,
,
.
0
(,
, , ) HYA. , , MFx ,
.
(9), Y = F SO3F,
HY + mMFx

HYMmFmx

, , SbF5
, . , ,
- , - SbF5 ,
( ) ( ) (. 1).
,
.
, . , Sb3F15 (
150C) Sb2F10 ( 250C).
SbF5 ,
H3O+SbF5OH.
, , , . SbF5
,
.
SbF5
. ,
SbF5 . ,
,
, .

(9)

HMmFmx + 1
( Y = F),
MFx SbF5 > AsF5 >
> TaF5 > BF3 > NbF5 > PF5 . MFx
HY

84

. , HFSbF5 (1 : 1),
HFSbF5 (9 : 1), HSO3FSbF5 (1 : 1) HSO3FSbF5
(5 : 1) 500 : 1 : 101 : 105.

. 1.

, 3, 1999

 (6) , HF, Hl, H2SO4 HSO3F,

.
, .
SO3 , H2SO4
H2S2O7 ,
H0 = 14,5. HAlCl4 HBF4 ,
HCl
AlCl3 HF BF3 , H0 = 1516.
HSO3F
SbF5 , (magic acid).

,
, , , .
,

,
.
.

HSO3FSbF5 ,
( 4 0) 100% HSO3F , 10% , :
HSO3F + SbF5

HSbF5SO3F,

(10)

H2SO3F+(SbF5SO3F) (11)

HSO3F + HSbF5SO3F

SbF5 90% 0
26,5
(12) (13)
, HSbmF5mSO3F:
mSbF5 + HSO3F

HSbmF5mSO3F,

(12)

HSbnF5nSO3F + HSbmF5mSO3F
H2SbnF5nSO3F+(SbmF5mSO3F),

(13)

n, m = 1, 2, 3,

n # m.

SbF5 5070%
(70%) SbF5SO3F
Sb2F10SO3F, SbF 6 SbF 4 ( SO 3 F ) 2 .
(14):
2SbF5SO3 F

SbF 4 ( SO 3 F ) 2 + SbF 6

(14)

,
(10)(14), . 2.
SbF5 . 1% SbF5 -

..

FSO2O

FSO2O

SbF 5 SO 3 F

OSO2F

SbF 4 (SO 3 F) 2

FSO2O

Sb 2 F 11

SbF 6

Sb 2 F 11 SO 3 F

FSO2O

Sb 3 F 16 SO 3 F

Sb 3 F 16

. 2. ,

0 11 100% HF 20,5.
HSO3F
25 SbF5 , 1
SbF5 HF 104
, HSO3F. HF : SbF5 = 1 : 1 0 ,
30, .

(15) SbF5 020% (16)
:
3HF + SbF 5
2HF + nSbF 5

H 3 F +2 SbF 6 ,

(15)

H 2 F + Sb n F 5n + 1

(16)

SbF5 HF , ,
. , , DHO D2O.
(, H2SO4)

H3O+ (1)
. , DH2O+ D2O+,
HSO3FSbF5 ,
:
D2O

+H+
H+

D2HO+
D+
+D+

D+
+D+

H2O

DHO
+H+
H+

+H+
H+

H3O+

DH2O+

D+
+D+

(17)

85

 HF
SbF5 .
, . , H3O+
, , :
D2HO+

+H+
H

D+

D2H2O2+
D+
+D+

+D

H3O+

DH2O+

+H+
H+

+H+
H

H4O2+

DH3O2+

D+
+D+

(18)

, H4O2+

(. 3), .
H
O2+

H
H

. 3. 42+

, , ,

. .

,

.
.
,
,
.
, . , ,

, , , (, ) , , .
, (I) -

86

,
(II) :
MLn

N+
MLn
I

HOMLn

N+
H
II

0 .
, ,
, . 100.
,
. ,

. , .
, , ,
.
:
.

0 $ 14,5
c 1N 500600.

() (- , )

, SO3H.
, , .

AlCl3 , (Ti, Fe, Ni, Cu, Mn, Al, Zr, Co, Mg,
Ca, Ba).
(Al2O3 , TiO2 , SiO2) (Al2O3SiO2 , TiO2ZrO2 , TiO2SiO2)
SbF5 . . 4 , Al2O3SiO2 , , ,

, 3, 1999

H
O

SbF5
SbF5

Si

Al

Si

. 4. ,

SbF5 . AlCl3 .
. 5.

,

,
() .
(Nafion-H) :

[ (CF2 CF2)m CF CF 2 ]n
[O CF 2 CFCF 3 ]k OCF2CF2 SO3H
. ,
,

. ,
, , ,
. (3,35 )
. , , ,
, , .
, (SbF5 , AsF5),
. , ,
, .
SbF5 . -

..

CH2

CH

CH2

Cl

Al

O S

Cl

CH2
+

CH H
CH2

. 5. ,

,
SbF5
, ,
.
(AlCl3 , AlBr3 .).
,
.

. , ,
,
, .

1. .. //
. 1996. 12. C. 3240.
2. .. . .: , 1977.

* * *
, , , .
, . . .
, .
250 .

87