Открыть Электронные книги
Категории
Открыть Аудиокниги
Категории
Открыть Журналы
Категории
Открыть Документы
Категории
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 , .
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
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