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, 2010, 51, 5, .

715727

541.127:546.98"386




(II)
2010 . . . , . . , . . , . . , . . ,
. . , . .
. ..
E"mail: olegtemkin@mail.ru
07.12.2009

n 
Pd(II). 
( HClO4 n) 
. 

. 
.



[1, 2] (
),
[3, 4] PdCl2 CuCl2
,


, 
, 
. 
(), 
PdCl2 CuCl2
(CuCl2O2)  (BQ)
[5, 6].

. . 1962 . [7],

() 
, ,
.. . [815].
PdSO4H2SO4 (HClO4)H2OBQ, 
(0.13.0 /
HClO4) 2030 
, PdSO4 [12, 13], 
. 
(PdSO4, Pd(OAc)2 c BQ ) 
[1618] 
[19] 
.
, l ClO 4


 ( 1 1) 
24 [H+] = 0.1 / ~60
[H+] = 0.3 / [17]. ,

. ,


40 [15], 
0.56 (Cl/Pd
20, HClO4 = 1.0 /, 298 K) [20].
Pd(OAc)2 

[16] 

(PcFe) [21].
[1015]
, , , 
.
1. 
Pd2+H+BQH2O 
(Pd(0) Pd 22+ ), 
. 

(, ).
Pd2SO4(BQ) 3H2O [22],
.
2.


, , 
, 

715

716

 Pd(0)(BQ)(CnH2n)2
 Pd(I) 
Pd(II),
Pd(BQ)(C2H4)2 + H+
Pd(C2H4)2(BQH)+.
 
Pd(0)(C2H4),
CH3CHO BQH2,
() 
, .. [4]

.
[1015]
 

[1618, 21].

.
1. 
Pd(II) 
. , 

SO 24 , NO3 OAc [17] (
). 
, Pd3(OAc)6 

Pd(CH3CN)4 ( H 2O)2x+.
2.

[H+] 
() . 
, 
, 

[2325].
, 
(r) [H+] 
r = a/[H+] [4]
. , 
"
PdCl2LiClHClO4H2O 
[20, 26]. 
[HCl]
0.52.0 / ([HCl + LiCl] = 5 /)
PdCl2HgCl2FeCl3
90 (r = b + a/[H+]) [27]. 
[H+] Cl : Pd <
< 20 2 [20],

[H+] 0.020.1 /.
Pd2+ 
[28] 
, 
( = 1.6)
[HClO4] = 0.1 / [Pd] = 0.004 / 
20%,

9%
0.2 /. 

, ,

,
1 [HClO4] = 0.10.3 /
2 [17]. 

[17] 

(II)
.
[6, 1018, 21]

/ [15] 


,
, 
[4, 29] .

(Q)
[30]. ,
Pd(I)

[31, 32], Pd(0) 
[33] o

[34, 35].


, Fe(II)
[3639]. 

(II)

[40].







 [30].


(23), 
,
10 . (
), n ( )
6
(7 : 1, . %). 
2 . 
(500 ), 
20

51

2010

. 2 
(
) () 
. 

. 
. 
1 ,
6 .
 :
8 ( , 
1 , Q,  
(1.7 /), 250, 
200,
180, 150 ( 
)), 8 ( ,
3 , , 
(1.35 /),
240, 150,
220, 140 (
)), (
, 3 , 
10% 4/ I, (0.33 /),
(0.03 /), (1.2 /),
300, 100).


Agilent Technologies 6890 N (),
 Agilent Technologies
5973 ( 1,
, 50 , 
0.32 , 0.51 ,
 (1 /),
100:1; :
50 (5 ),
15 / (12 ), 230 (5 );
0.2 ).

( )
JEOL JEM 2100. 
. 
, 
25 .


. 
,
(
[41]
.. ), .

Acrosorganics, 
n.
[42].


[43]


51

2010

717

[S], /
0.16
0.12

0.08
0.04

20

40

60
t,

. 1. [S]
.
. [Pd]0 = 0.004 /, [Q]0 = 0.2 /,
[HClO4] = 0.2 /.


STIFF [44],
ATX (
95). 

[43]

, 

, ..
.


. 
, 

. 





. 

. ,


4 /, 
(. 1).

(I) BQ 
Q
C6H10 + H2O + Q
C6H10O + QH2
(I)
Pd(OA)2HClO4H3NH2O 
[45]*, Pd(II)
* 
.. .

718

[S], /
0.16

[S], /
0.16

0.12

0.12

4, 4'

0.08

0.08

0.04

0.04
1, 1'
1, 1'

10

20

30

40

50

60
t,

. 2. 
[Pd]0. [Pd]0, /: 1 0.004 (1'
1), 2 0.002, 3 0.0015;
[Q]0 = 0.4 /, [HClO4] = 0.2 /.

0.0010.005 / HClO4 0.10.5 /,


: ,
2.4, [1618], 
2025 
(. 1).
(S)
() (95
100%).
21 21.

, ,
.
Pd(OAc)2 0.05 / 2
1 13%.
Pd(OA)2 (0.05 /)HClO4 (0.2 /)BQ
(0.2 /)S (0.06 /)H3NH2O 
, Pd(OA)2H3NH2O 
.
Pd(OA)2BQ
.
Pd(OA)2HClO4S
, , 
.
Pd(OA)2HClO4.
,


(. 1 2).
, 
[Pd]0, [S]0, [H+]0 [Q]0. 

([S]),
( 
) 
(. 3).

10

20

30

40

50
60
t,

. 3. 
[Pd]0. [Pd]0, /:
1 0.004 (1' 1), 2 0.002,
3 0.0015, 4 0.001 (4' 4);
[Q]0 = 0.4 /, [HClO4] = 0.2 /.


( 2.6 )

(1) (2)
[S]
d[S]/dt = k[S]n,

(1)

d[S]/dt = k[S]n/(1 + k1[S]m),

(2)


. 

[S] (SS)
(1) n = 2.
, (2),
n m
n = 2 m = 0.2.
([Q] = a + [S], = [Q]0 [S]0) (1) (2)
d[S]/dt = k[S]n[Q]m = k[S]n(a + [S])m,

(3)

d[S]/dt = k[S]n(a + [S])/(1 + k1[S]m)

(4)


(3) , . 1,
n = 1 m = 1 (a = 0.05), SS 
= 0.25 n = 2 m = 1 
. 2.
(4) .
, 
.

( )
+ BQ.
r0 [H+]0 (. 4) 
[HClO4] + [LiClO4] = 0.7 /. 
r0
[17]

51

2010

[H+] = 0 [H+]0 
[H+] = 0.40.5 /.
(r) 
[H+]0.

[BQ]0 =
= 0.4 /
(. 5). r ,
[H+]0, [BQ]0.



(I). 
2,6()"
,
, 
,
(. 6). 2,6
, 2,31,4, 
, 
.
,
[S], [H+]0,
[BQ]0  


(II) [14, 15] , 
(I)

 [4].
Pd(II)

S, H2O
P

Pd(0)

BQ, H+
BQH2

Pd(II).

Pd(II)

Pd(II)S

BQ, H2O
P

r0, 1 1
0.06
0.04
0.02

0.1 0.2 0.3 0.4 0.5 0.6 0.7


[HClO4], /

. 4.
(r0) [H+]0 . [HClO4] +
+ [LiClO4] = 0.7 /, [Pd]0 = 0.004 /, [Q]0 =
= 0.2 /, [S]0 = 0.15 /.

r0, 1 1
0.08
0.06
0.04
0.02
0

(II)


, BQ 
,

719

0.1 0.2 0.3 0.4 0.5 0.6


[BQ], /

. 5.
. [Pd]0 = 0.004 /,
[HClO4] = 0.2 /, [S]0 = 0.15 /.

H+

Pd(0)BQ BQH2 Pd(II),(III)

,
Pd(0)BQ

, 
[S]t, rt[S] ( 
), r0[BQ]0
r0[H+]0. , r0 [BQ]0 
,
[BQ]0 
[H+] 1 [S]0.
( ) 
,
(III) 
,

. (III)
, 

Pd(II) Pd(0), Pd(II) Pd(I), Pd(I)

51

2010

[S], /
0.16
0.12
1
2
3

0.08
0.04

10

20

30

40

50

60 70
t,

. 6.  
.
[Pd]0 = 0.004 /, [HClO4] = 0.2 /, [Q]0 =
= 0.2 /. 1 2,6(),
2 , 3 .

720

.
r0, 1 1
0.10

[Pd]0 00.002 /. 
S
[Pd]0 (. 3).

0.08

r0 [Pd]0 , 
, 

[30]
[3639] 




, 
,
BQ ,


Pd(0) Pd 22+ . 


([M]0) [30]. 
,
, 
>1 .
Pd [41] 26.0 3.5
.

0.06
0.04
0.02
0

0.002

0.004
0.006
[Pd]0, /

. 7.
[Pd]0. Q]0 = 0.004 /, [HClO4] = 0.2 /,
[S]0 = 0.15 /.

Pd(0)

.




. ,


([S]0/[Pd]0 15 [30]) 

6080%.

[Pd]0 (. 2) , 
S
[Pd]0 
0.0010.006 / (. 7)
M + P,

M+S
M + S

M + P,

M + S

M + P,

M + S

M + P,
1.40

[BQ] =
= 0.4 / (. 2). 1.50 
Pd 22+ , 
Pd2+.

( 1.31.5)
M + P,

..
, 

M + P,

, 1.301.50

2M + S

1.30

M+S



( ),




, ,

2M + P,

M+S
M + S

M + P
1.50

. 2 ( 
SS ( )

) 1.3 1.5: 1.3 (0.236
104) 1.5 (0.23 104) < 1.4 (0.86 104).

.
1.31.5 

M + S

MS
51

2010

Pd2+

S
(2)

(1)

Pd0

Pd2+

(3)

(1)

1.31.5 
, ,

Pd2+, S
(2)

1.3

Pd22+

Pd2+

(3)

(1)

S
(2)

Pd2+

Q
P

X1

2 Pd0
(3)

1.4



1.31.5 

1.5

Q ([Q])
1.321.52.

Pd0Q

X2

,
P

Q
S

Pd2+

Pd2+, Q
P

P
S, Q
P

Q
P

X1

Q
P

1.4M2

1.5M2

X2

P
S

X2

2 Pd0Q

Q
Pd2Q2+

P
X1

1.3M2

Pd2Q2+

Pd2Q2+

2 Pd2+

X1

Q
2 Pd0Q

X2

.
P

1.53 
[Pd2Q]2+ Pd2+.


[Pd]0 [Q]0. SS ( )
:
1.53 (0.05 104) < 1.32 (0.12 104) <
< 1.52 (0.66 104) < 1.42 (1.0 104).
,

, :
1.53 (0.67 104) < 1.32 (1.43 104)
1.52 (1.44 104) < 1.42 (1.79 104)
1.53.
6

51

2010

721

1.5M3

1.31.5 1.32
1.53 ,
, 


, 
, 
10100 , . 
,

, 
8 20 
, 
.
, 


.

722

.
[S], /
0.16
0.14
0.12
4

0.10
0.08

0.06

0.04
0.02

10

20

30

40

50

60

70
t,

. 8. 
. , . [Pd]0, /: 1 0.004, 3 0.002, 4 0.0015, [Q]0 = 0.4 /; 2
0.004, [Q]0 = 0.2 /, [HClO4] = 0.2 /.


M , .. 
" 

(, Pd2+). 
,
1.53
3.1.53.
(7)

2 Pd2+
S, Q (1)
P

3.1.5M3
Pd2Q2+

S
(2)

X1

Q
P
(4)

Pd0Q

X2

(6)

(3)

S
(5)

3.1.53 
,
,

. 
3.1.53 
Pd(I)
Pd(II) Pd(0)
Pd(I)
(8)

Pd2Q2+ + 2H+

(9)

PdQ0 + Pd2+

2Pd2+ + QH2,
Pd2Q2+

(9), ..
Pd(I), 
4.1.53. 5
(

4.1.53)
( )
(. 8),

(. 9). SS 
0.17 104, .. 4.1 /,
. (9)

3.6 104 / ( 

). [46] 
(II) 
,
.

, 
4.1.53 
,
:
1) (8)
Pd(I), 
1( (1) (8))
;
2)
Pd(II) Pd(I) Pd(0),

5 , ,
2 ( (2) (3)) 3 ( (5)
(6)),
2.
4 ( (1), (2), (4) (7)) 5 (
(1), (7) (9));

51

2010

3) 
PdQ0
1. 2 3
, rP2 rP3
23 ;
4) (73 )

Pd(0), Pd(0) Pd(I) 
.
73 , , 
, 90 
Pd Pd(II), 76

Pd(I);
5) 

,
[S] (. 2 3).

,
[S],  
, (2)(3),
.
( 80%);
6) 
0.0015 0.004 /

(. . 3). 
, 


.
, (II) 
, ,
Pd(0)
Pd(I), (9). ,

.



Pd2+, Pd 22+ Pd0
,


, , .

, 

Pd2+

QH2

PdS2+

2H+
QH2

51

0.12

0.09
0.06

0.03
0

25

PdQ0
5

2010

50

75

100

125
t,

. 9. 
. [Pd]0 = 0.004 /,
[Q]0 = 1.05 (1) 0.85 / (2), [HClO4] =
= 0.2 /.

, 
, . 
[Pd(CH3CN)4]2+

[Pd2(CH3CN)6]2+ [47].
Pd2SO4(BQ) [22]. 
LPdQ [48] (L 1,5, Q

"),
[L2Pd(2Q)]2(QH2)
2
2
MeOH L2Pd2( , Q)2 MeOH [34, 35] (L
PPh3, Q ). ,
( 
) CH3CNH2OH+Q

(II), (I) (0).
[49] 
 
, Pd(II)
Pd(0). [4],
, 
 
Pd2+ (
, 
~PdCH2CH2OH 2+ ), 
( 
) Pd2+,
Pd 22+ Pd(0) , 
[1015].
Pd2+(SC2H4).
(IV) 2 ,
[Pd2Q]2+ Pd2+:

PdCH2CH2O+H2

P
2H+ Q

[S], /
0.15

QH2 2H+

H2O +

723

Pd2+
P
2H+

Pd22+

Pd2Q2+

(IV)

Pd2+

6*

724

[Pd2Q]2+.

[Pd2Q]2 +:
H+
QH2

Pd2Q2+

HQPd2Q+
P Q
HO
Pd2Q(S)2+ H2 +

QPd2R+

QH2 H+

HQPd2Q+

H+

P
Q
H+

(V)

Pd2Q2

R = CH2CH2OH

Pd2Q2 
Pd0Q
2Pd0Q ,

Pd2Q2


(IV) (V).
Pd0Q.
Pd0Q

Pd0Q(S)

H+

HQPdS+

H2O
H+

HQPdR (VI)

Q
P, QH2

(IVVI) , 
Pd0Q [Pd2Q]2+ 
, 
Pd2+
(IV) 
Pd0Q [Pd2Q]2+ , , 
.

[PdCl4]2,
(I) 

c [4].

+
PdCH2CH2O+H2 
,
[PdL4]2+,
Pd 22+ 
Pd0Q.
(IV) (V) 
,
, .. 
( 
)
( )
(.. ,
.. ).
n, 
, 
.. [50, 51].

[Pd(CH3CN)4]2+ [Pd(CH3CN)4 x(H2O)x]2+ ,

, 
 
, 

( 
)
[PdL4]2+ .

Pd3(OAc)6

[52, 53] 
e [5456] ( ). 
, ,


[5457] 
[58] 
,
 

[40].


Hg2+ [5963], ,

(II) [63]. 

, 

[6466].
(II) 
298,
1.5 104 / 
+, , ,

+HgCH2CH2+2 , 
, [66].
, 

, 
[4] ( IV),
, 

 
(II) ().
1 
21 12,

2 ( 
[4]) 
Pd2+ 3 .
 
1 2, ,

(II)
[20, 26] (.  Pd

 ,

51

2010

6
1 2

9
+

O+H2
PdH 8

Pd

OH2

H3O

H+

Pd

3

5
2
+

OH
OH2

OH2

Pd2+

H+

H+

H2O

OH 6

4
PdH+

Pd

(H+)
Pd0

H3O+

Pd

H2O

H2O

6
+

Pd0

+PdH

PdH+

H3O+

+
Pd O H2

725

H2O

2H+

Pd0
H2O

H+

(.. ) 12 
21 
.  (II).

50  [67]). 
1 1 3 , 
, 4 5 
. 4 (, 
2 ) 5 (
6) 
.
6  PdH+ 
16 1. , 
 PdH+ 12
1
 PdH+
8 1 9,
 [4, 68], 1 

 Pd2+. 32 
 1
(3
1),
, 
7,
 7 PdH+,
. 1, 3, 4
5  
Pd2+ 
Pd0Q [Pd2Q]2+, .. 

51

2010


Pd(II) (. (IV)).



,

Pd2+ 
(I) (0).




, 
[H+]
, 
Pd2+,

, 

. 


, 

[69].

726


( 070300315).
.. 
..
, ..

. .. 
 
.

1. Smidt J., Hafner W., Jira R., Sedlmeier J., Sieber R.,
Ruttinger R., Kojer H. // Angew. Chem. 1959. B. 71.
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. .: , 1970.
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. 1969. . 10. 4. C. 717.
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. 1970. . 11. 5. . 1152.
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. 1971. . 12. 6. . 1417.
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. . . . 1973. 1. . 25.
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. 1977. . 18. 2. . 380.
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veev K.I. // Appl. Catal. A. General. 2007. V. 319. P. 91.
14. .., .., .. // 
. 1976. . 17. 4. . 893.
15. .., .., .. // 
. 1981. . 22. 6. . 1451.
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19. Monflier E., Blouet E., Barbaux Y., Mortreux A. // An
gew. Chem. Int. Ed. 1994. B. 33. 20. S. 2100.
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P. 399.
21. Bckvall J."E., Hopkins R.B. // Tetrahedron Lett. 1988.
V. 29. 23. P. 2885.
22. .., .., .., "
.., .. // . .
. . 1973. 7. C. 1453.

23. Davidson J.M., Triggs C. // J. Chem. Soc. A. 1968. 6.


P. 1324.
24. Clark F.R.S., Norman R.O.C., Tomas C.B., Willson J.S. //
J. Chem. Soc. Perkin Trans 1. 1974. 11. P. 1289.
25. .., .., .. //
. . . . 1979. 1. C. 242.
26. .., .., .. // .
. 1961. . 139. . 3196.
27. .., .., ..,
.. // . 1981. . 22.
6. . 1446.
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.
.: , 1979. 192 .
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Chem. Soc. 1974. V. 96. 4. P. 1003.
30. .. 
. . .: ,
2008. 918 .
31. " .., .. // 
. 1985. . 25. 2. . 316.
32. " .., .. // 
. 1985. . 25. 2. . 325.
33. Roffia P., Gregorio G., Conti F., Ugo R., Pregaglia G. //
J. Mol. Catal. 1977. V. 2. P. 191.
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Belsky V.K., Zavodnik V.E. // Mendeleev Commun.
2002. . 12. 2. P. 47.
35. .., .., .., "
.., .., .., .. //
. . . . 2007. 2. . 244.
36. .., .., .. //
. . . 1996. . 66. 5. . 716.
37. .., .. // . . .
1997. . 67. 10. . 1606.
38. .., .., .., "
.. // . 2004. . 45. 3.
. 407.
39. .. // . . . . 2007. 5.
C. 842.
40. .., .., .., "
.. // . . . 2002. . 72. 6.
. 1004.
41. .., .. // .
1995. . 64. 1. . 51.
42. Stephenson T.A., Morehouse S.M., Powell A.R., Hef"
fer J.P., Wilkinson G. // J. Chem. Soc. 1965. P. 3632.
43. .., .. //
.
1982. . 68. 5 (98). . 47.
44. .., .. STIFF

. .:  . 
, 1977. 43 .
45. Temkin O.N., Bruk L.G., Petrov I.V., Zakharova D.S. //
16th Int. Symp. on Homogeneous Catalysis. Book of
Abstracts. Florence, Italy, 2008. P021.
46. .., .., ..,
.., .., .. // 
. 1982. . 23. 6. C. 1494.

51

2010


47. Murahashi T., Nagai T., Okuno T., Matsutani T.,
Kurosawa H. // J. Chem. Soc., Chem. Commun.,
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