УДК 539.143.43+547.244+519.27 ИСПОЛЬЗОВАНИЕ

Раздел 2
553
ɍȾɄ 539.143.43+547.244+519.27
ɂɋɉɈɅɖɁɈȼȺɇɂȿ ɄɈɊɊȿɅəɐɂɃ əɆɊ 11ȼ ȾɅə
ɈɉɊȿȾȿɅȿɇɂə ɉɈɅɈɀȿɇɂə ȽȺɅɈȽȿɇɈȼ ȼ
ȽȺɅɈȽȿɇɉɊɈɂɁȼɈȾɇɕɏ
7,8-ȾɂɄȺɊȻȺ-ɇɂȾɈ-ɍɇȾȿɄȺȻɈɊȺɌ(-1) ȺɇɂɈɇȺ
Ɋɭɞɚɤɨɜ Ⱦ.Ⱥ., ɉɨɬɤɢɧ ȼ.ɂ., ɋɤɚɤɨɜɫɤɢɣ ȿ.Ⱦ.
ɂɧɫɬɢɬɭɬ ɮɢɡɢɤɨ-ɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɇȺɇ Ȼɟɥɚɪɭɫɢ, Ɇɢɧɫɤ
ɋɩɟɤɬɪɨɫɤɨɩɢɹ əɆɊ 11ȼ — ɞɨɫɬɭɩɧɵɣ ɢ ɷɮɮɟɤɬɢɜɧɵɣ ɦɟɬɨɞ
ɭɫɬɚɧɨɜɥɟɧɢɹ ɫɬɪɭɤɬɭɪɵ ɩɪɨɢɡɜɨɞɧɵɯ ɨɪɬɨ-ɤɚɪɛɨɪɚɧɚ. ɂɫɫɥɟɞɨɜɚɧɢɟ
ɤɥɚɫɬɟɪɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɛɨɪɚ ɦɟɬɨɞɨɦ əɆɊ 11ȼ ɩɨɡɜɨɥɢɥɨ
ɫɮɨɪɦɭɥɢɪɨɜɚɬɶ ɪɹɞ ɩɪɚɜɢɥ ɢ ɡɚɤɨɧɨɦɟɪɧɨɫɬɟɣ ɜ ɫɩɟɤɬɪɚɯ [1,2],
ɭɫɬɚɧɨɜɢɬɶ ɜɥɢɹɧɢɟ ɡɚɦɟɫɬɢɬɟɥɟɣ ɧɚ ɯɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ ɜ ɤɥɚɫɬɟɪɧɨɦ
ɨɫɬɨɜɟ ɢ ɩɪɟɞɥɨɠɢɬɶ ɪɹɞ ɤɨɪɪɟɥɹɰɢɨɧɧɵɯ ɡɚɜɢɫɢɦɨɫɬɟɣ [3]. ɐɟɥɶɸ
ɞɚɧɧɨɣ ɪɚɛɨɬɵ ɹɜɥɹɟɬɫɹ ɜɵɹɜɥɟɧɢɟ ɤɨɪɪɟɥɹɰɢɨɧɧɵɯ ɡɚɜɢɫɢɦɨɫɬɟɣ,
ɭɞɨɛɧɵɯ ɞɥɹ ɧɚɞɟɠɧɨɝɨ ɢ ɞɨɫɬɨɜɟɪɧɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ ɩɨɥɨɠɟɧɢɹ
ɝɚɥɨɝɟɧɨɜ ɜ ɨɫɬɨɜɟ ɫɢɦɦɟɬɪɢɱɧɵɯ ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ 7,8-ɞɢɤɚɪɛɚɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬ(-1) ɚɧɢɨɧɚ ɧɚ ɨɫɧɨɜɚɧɢɢ ɞɚɧɧɵɯ əɆɊ 11ȼ.
ɉɪɨɚɧɚɥɢɡɢɪɨɜɚɧɵ ɫɩɟɤɬɪɵ əɆɊ 11ȼ ɚɥɤɢɥɚɦɦɨɧɢɣɧɵɯ ɫɨɥɟɣ
+
(Me4N , Me3NH+) ɪɚɡɥɢɱɧɵɯ ɦɨɧɨ- ɢ ɞɢɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ 7,8ɞɢɤɚɪɛɚ-ɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬ(-1) ɚɧɢɨɧɨɜ: Kt+[9,11-X2-7,8-R2-7,8-C2B9H8](X = Cl, Br, I; R = H, CH3 [4]), Kt+[5,6-X2-7,8-C2B9H10]- (X = Cl, Br [5], I),
Kt+[2,4-I2-7,8-C2B9H10]- [6], Kt+[3-X-7,8-C2B9H11]- (X = Br [7], I [7]) (Kt =
ɚɥɤɢɥɚɦɦɨɧɢɣɧɵɣ
ɤɚɬɢɨɧ)
ɢ
H
ɨɛɧɚɪɭɠɟɧɵ
ɥɢɧɟɣɧɵɟ
ɤɨɪɪɟɥɹɰɢɨɧɧɵɟ
ɡɚɜɢɫɢɦɨɫɬɢ
10
ɯɢɦɢɱɟɫɤɢɯ
ɫɞɜɢɝɨɜ
ɫɢɝɧɚɥɨɜ
11
9
ɚɬɨɦɨɜ
ɛɨɪɚ,
ɫɜɹɡɚɧɧɵɯ
ɫ
8
7
C
C
ɝɚɥɨɝɟɧɚɦɢ
G(ȼn,m)-Hal,
ɨɬ
6
ɯɢɦɢɱɟɫɤɢɯ
ɫɞɜɢɝɨɜ
ɫɢɝɧɚɥɨɜ
5
3
2
4
ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ
ɧɟɡɚɦɟɳɟɧɧɵɯ
ɚɬɨɦɨɜ
ɛɨɪɚ
ɢɫɯɨɞɧɵɯ
1
ɤɚɪɛɨɪɚɧɨɜɵɯ
ɚɧɢɨɧɨɜ
G(ȼn,m).
Ɋɢɫ. 1. Ⱥɧɢɨɧ [7,8-ɋ2ȼ9ɇ12]
ɋɬɪɨɟɧɢɟ ɢ ɧɭɦɟɪɚɰɢɹ ɚɬɨɦɨɜ 7,8ɞɢɤɚɪɛɚ-ɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬ(-1) ɚɧɢɨɧɚ ɩɪɟɞɫɬɚɜɥɟɧɵ ɧɚ ɪɢɫɭɧɤɟ 1.
ȼɫɟ ɪɚɫɫɦɚɬɪɢɜɚɟɦɵɟ ɫɨɟɞɢɧɟɧɢɹ, ɤɚɤ ɨɩɢɫɚɧɧɵɟ ɜ ɥɢɬɟɪɚɬɭɪɟ,
ɬɚɤ ɢ ɩɨɥɭɱɟɧɧɵɟ ɧɚɦɢ ɜɩɟɪɜɵɟ, ɫɢɧɬɟɡɢɪɨɜɚɧɵ ɫɥɟɞɭɸɳɢɦɢ
ɦɟɬɨɞɚɦɢ.
554
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1. ȼɟɳɟɫɬɜɚ, ɫɨɞɟɪɠɚɳɢɟ ɝɚɥɨɝɟɧɵ ɜ ɨɬɤɪɵɬɨɣ ɩɥɨɫɤɨɫɬɢ ɋ2ȼ3 ɜ
ɩɨɥɨɠɟɧɢɹɯ ȼ(9,11), ɩɨɥɭɱɚɥɢ ɞɟɣɫɬɜɢɟɦ ɝɚɥɨɝɟɧɢɪɭɸɳɢɯ ɚɝɟɧɬɨɜ ɧɚ
ɫɨɥɢ 7,8-ɞɢɤɚɪɛɚ-ɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬɨɜ (ɪɢɫ. 2).
2. ɋɨɟɞɢɧɟɧɢɹ, ɫɨɞɟɪɠɚɳɢɟ ɝɚɥɨɝɟɧɵ ɜ ɡɚɤɪɵɬɨɣ ɩɟɧɬɚɝɨɧɚɥɶɧɨɣ
ɩɥɨɫɤɨɫɬɢ ɜ ɩɨɥɨɠɟɧɢɹɯ ȼ(5,6), ɩɨɥɭɱɟɧɵ ɩɨ ɪɟɚɤɰɢɹɦ ɞɟɛɨɪɢɪɨɜɚɧɢɹ
ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ ɨɪɬɨ-ɤɚɪɛɨɪɚɧɨɜ (ɪɢɫ. 3),
ɚɧɚɥɨɝɢɱɧɨ ɩɨɥɭɱɟɧɵ ɢ ȼ(3)-ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɟ.
3. ɋɨɟɞɢɧɟɧɢɟ ɫ ɚɬɨɦɚɦɢ ɢɨɞɚ ɜ ɩɨɥɨɠɟɧɢɹɯ ȼ(2,4)
ɫɢɧɬɟɡɢɪɨɜɚɧɨ
ɜ
ɫɨɨɬɜɟɬɫɬɜɢɢ
ɫ
ɦɟɬɨɞɨɦ
ɩɪɟɞɥɨɠɟɧɧɵɦ
Ɋɚɦɚɱɚɧɞɪɚɧɨɦ-Ʉɧɨɛɥɟɪ-ɏɨɬɨɪɧɨɦ, ɩɨ ɫɯɟɦɟ, ɩɪɟɞɫɬɚɜɥɟɧɧɨɣ ɧɚ ɪɢɫ. 4.
H
H
R C
C
R
10
ɤɢɩɹɱɟɧɢɟ
11
C
KOH, EtOH R
6
2
C
5
3
X
[X]
9
8
7
R
4
C
2
6
X
9
8
7
R
R = H, CH3
X = Cl, Br, I
10
11
C
3
5
R
4
1
1
Ɋɢɫ. 2. Ɇɟɬɨɞ ɩɨɥɭɱɟɧɢɹ ȼ(9,11)-ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ [7,8-ɋ2ȼ9ɇ12]H
C
X
X
11
7
ɤɢɩɹɱɟɧɢɟ
C
C
KOH, EtOH
3
X = Cl, Br, I
8
2
10
9
C
4
1
6
5
X
X
Ɋɢɫ. 3. Ɇɟɬɨɞ ɩɨɥɭɱɟɧɢɹ ȼ(5,6)-ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ [7,8-ɋ2ȼ9ɇ12]H
I
10
11
C
2
6
9
8
7
C
3
1
5
4
I
BHCl2;SMe2
I ɤɢɩɹɱɟɧɢɟ
I
C
C
10
11
C
KOH, EtOH
I
2
6
9
8
7
C
3
5
4
I
1
Ɋɢɫ. 4. Ɇɟɬɨɞ ɩɨɥɭɱɟɧɢɹ ȼ(2,4)-ɢɨɞɩɪɨɢɡɜɨɞɧɨɝɨ [2,4-I2-7,8-ɋ2ȼ9ɇ10]ȼɫɟ ɩɪɨɢɡɜɨɞɧɵɟ 7,8-ɞɢɤɚɪɛɚ-ɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬ(-1) ɚɧɢɨɧɨɜ
ɜɵɞɟɥɟɧɵ ɜ ɜɢɞɟ ɚɥɤɢɥɚɦɦɨɧɢɣɧɵɯ ɫɨɥɟɣ.
Раздел 2
555
ɋɩɟɤɬɪɵ əɆɊ 11ȼ ɜɟɳɟɫɬɜ, ɩɨɥɭɱɟɧɧɵɯ ɧɚɦɢ, ɡɚɩɢɫɵɜɚɥɢɫɶ ɧɚ
ɫɩɟɤɬɪɨɦɟɬɪɟ AVANCE-500 (ɪɚɛɨɱɚɹ ɱɚɫɬɨɬɚ 160.4 ɆȽɰ) ɜ ɪɚɫɬɜɨɪɟ
ɚɰɟɬɨɧɚ-d6. ȼ ɤɚɱɟɫɬɜɟ ɷɬɚɥɨɧɚ ɫɪɚɜɧɟɧɢɹ ɢɫɩɨɥɶɡɨɜɚɥɢ BF3˜OEt2.
ɋɩɟɤɬɪɵ ɜɟɳɟɫɬɜ, ɨɩɢɫɚɧɧɵɯ ɜ ɥɢɬɟɪɚɬɭɪɟ, ɡɚɩɢɫɚɧɵ ɧɚ ɫɩɟɤɬɪɨɦɟɬɪɚɯ
Bruker ARX 300 ɢ ɧɚ Bruker ARX 500.
ɂɡ ɤɨɪɪɟɥɹɰɢɨɧɧɨɣ ɡɚɜɢɫɢɦɨɫɬɢ (ɪɢɫ. 5) ɜɢɞɧɨ, ɱɬɨ ɩɪɢɪɨɞɚ
ɝɚɥɨɝɟɧɚ ɜɥɢɹɟɬ ɧɚ ɯɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɚɬɨɦɨɜ ɛɨɪɚ.
ȼɜɟɞɟɧɢɟ ɚɬɨɦɚ ɢɨɞɚ ɫɦɟɳɚɟɬ ɯɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ ɚɬɨɦɨɜ ɛɨɪɚ ɜ ɨɛɥɚɫɬɶ
ɫɢɥɶɧɨɝɨ ɦɚɝɧɢɬɧɨɝɨ ɩɨɥɹ, ɚ ɜɜɟɞɟɧɢɟ ɚɬɨɦɨɜ ɛɪɨɦɚ ɢ ɯɥɨɪɚ, ɧɚɨɛɨɪɨɬ,
ɜ ɨɛɥɚɫɬɶ ɫɥɚɛɨɝɨ ɦɚɝɧɢɬɧɨɝɨ ɩɨɥɹ. ȼɥɢɹɧɢɟ ɤɚɬɢɨɧɨɜ ɧɚ ɯɢɦɢɱɟɫɤɢɟ
ɫɞɜɢɝɢ ɧɟɡɧɚɱɢɬɟɥɶɧɨ ɢ ɧɚɦɢ ɧɟ ɪɚɫɫɦɚɬɪɢɜɚɥɨɫɶ. ɇɚɣɞɟɧɧɵɟ
ɡɚɜɢɫɢɦɨɫɬɢ
ɩɨɡɜɨɥɹɸɬ
ɨɩɪɟɞɟɥɹɬɶ
ɩɨɥɨɠɟɧɢɹ
ɝɚɥɨɝɟɧɨɜ,
ɩɪɨɝɧɨɡɢɪɨɜɚɬɶ ɯɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ ɫɢɝɧɚɥɨɜ ɚɬɨɦɨɜ ɛɨɪɚ, ɫɜɹɡɚɧɧɵɯ ɫ
ɝɚɥɨɝɟɧɚɦɢ ɜ ɤɚɪɛɨɪɚɧɨɜɨɦ ɨɫɬɨɜɟ.
ɏɢɦɢɱɟɫɤɢɣ ɫɞɜɢɝ ɡɚɦɟɳɟɧɧɵɯ ɚɬɨɦɨɜ
ɛɨɪɚ (B-X, X = Cl, Br, I), ɦ.ɞ.
-
[n,m-X2-7,8-R2-7,8-C2B9H8]
n ɢ m = 9 ɢ 11, X = Cl, Br, I
n = 3, X = Br, I
n ɢ m = 2 ɢ 4, X= I
n ɢ m = 5 ɢ 6, X = Cl, Br, I
20
10
R = H, Me;
R = H;
R = H;
R = H.
Cl
Br
I
0
-10
-20
-30
-40
B(2,4) B(3) B(5,6) B(9,11)
-50
-35
-30
-25
-20
-15
-10
-5
ɏɢɦɢɱɟɫɤɢɟ ɫɞɜɢɝɢ ɚɬɨɦɨɜ ɛɨɪɚ ɚɧɢɨɧɨɜ
[7,8-R,R-7,8-C2B9H10] (R = R = H, Me), ɦ.ɞ.
Ɋɢɫ. 5. Ʉɨɪɪɟɥɹɰɢɨɧɧɚɹ ɡɚɜɢɫɢɦɨɫɬɶ ɦɟɠɞɭ G(ȼ[n,m]) ɢ G(ȼ[n/m]-Hal)
Ⱦɨɩɨɥɧɢɬɟɥɶɧɨ, ɞɥɹ ɨɞɧɨɡɧɚɱɧɨɝɨ ɨɩɪɟɞɟɥɟɧɢɹ ɩɨɥɨɠɟɧɢɹ
ɝɚɥɨɝɟɧɨɜ, ɛɵɥɢ ɡɚɩɢɫɚɧɵ ɫɩɟɤɬɪɵ əɆɊ 11ȼ{1H} ɢ 11ȼ, ɚ ɬɚɤɠɟ
ɞɜɭɦɟɪɧɵɟ ɫɩɟɤɬɪɵ əɆɊ 11ȼ-11ȼ COSY ɞɢɝɚɥɨɝɟɧɞɢɦɟɬɢɥɶɧɵɯ
ɩɪɨɢɡɜɨɞɧɵɯ Kt+[9,11-X2-7,8-(ɋɇ3)2-7,8-C2B9H8]- (X = Cl, Br, I [ɪɢɫ. 6]).
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3
5,6 2,4 9,11
10
1
-35.0
-30.0
-25.0
-20.0
-15.0
-10.0
ppm (t1
-10.0
ppm (t2)
-15.0
-20.0
-25.0
-30.0
-35.0
Ɋɢɫ. 6. ɋɩɟɤɬɪ əɆɊ 11ȼ-11ȼ COSY Me3NH+[9,11-I2-7,8-(ɋɇ3)2-7,8C2B9H8]Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɧɚɦɢ ɩɪɟɞɥɨɠɟɧɵ ɤɨɪɪɟɥɹɰɢɨɧɧɵɟ ɡɚɜɢɫɢɦɨɫɬɢ,
ɭɞɨɛɧɵɟ ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɩɨɥɨɠɟɧɢɹ ɝɚɥɨɝɟɧɨɜ ɜ ɫɢɦɦɟɬɪɢɱɧɵɯ
ɝɚɥɨɝɟɧɩɪɨɢɡɜɨɞɧɵɯ 7,8-ɞɢɤɚɪɛɚ-ɧɢɞɨ-ɭɧɞɟɤɚɛɨɪɚɬ(-1) ɚɧɢɨɧɚ, ɧɚ
ɨɫɧɨɜɚɧɢɢ ɞɚɧɧɵɯ əɆɊ 11ȼ.
Ʌɢɬɟɪɚɬɭɪɚ
1. Hermanek S. // Chem. Rev. – 1992. - V. 92. - ʋ 2. - P. 325 - 362.
2. Hermanek S. // Inorg. Chem. Acta. – 1999. - V. 289. - P. 20 - 44.
3. ɉɨɬɤɢɧ ȼ.ɂ., ɒɢɪɨɤɢɣ ȼ.Ʌ., Ɋɭɞɚɤɨɜ Ⱦ.Ⱥ., ɋɤɚɤɨɜɫɤɢɣ ȿ.Ⱦ. //
ɋɬɪɭɤɬɭɪɚ ɢ ɞɢɧɚɦɢɤɚ ɦɨɥɟɤɭɥɹɪɧɵɯ ɫɢɫɬɟɦ: ɋɛ. ɫɬɚɬɟɣ. ȼɵɩ. XIII,
ɑ. II. – ɍɮɚ: ɂɎɆɄ ɍɇɐ ɊȺɇ – 2006. – ɫ. 137 - 140.
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