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 Структура и динамика молекулярных систем, 2007 г., Выпуск №1 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 BF3OEt2. 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]). 556 Структура и динамика молекулярных систем, 2007 г., Выпуск №1 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. 4. Ɋɭɞɚɤɨɜ Ⱦ.Ⱥ., ɉɨɬɤɢɧ ȼ.ɂ., Ⱦɢɤɭɫɚɪ ȿ.Ⱥ., ɉɟɬɪɨɜɫɤɢɣ ɉ.ȼ., ɋɢɜɚɟɜ ɂ.Ȼ., Ȼɪɟɝɚɞɡɟ ȼ.ɂ. // ɂɡɜ. ɊȺɇ, ɫɟɪ. ɯɢɦ. 2007. - ʋ 5. ɫ. 887 890. 5. ɉɨɬɤɢɧ ȼ.ɂ., Ɋɭɞɚɤɨɜ Ⱦ.Ⱥ., Ɂɚɥɟɫɫɤɚɹ ȿ.Ƚ., ɒɢɪɨɤɢɣ ȼ.Ʌ. // Ⱦɨɤɥɚɞɵ ɇȺɇ Ȼɟɥɚɪɭɫi. 2007. - Ɍ. 51. - ʋ1. - ɫ. 63 - 66. 6. Ramachandran B.M., Knobler C.B., Hawthorne M.F. // Inorg. Chem. 2006. - V. 45. - ʋ 1. - P. 336 340. 7. Barbera G., Vinas C., Teixidor F., Welch A.J., Rosair G.M. // J. Organometal. Chem. 2002. - V. 657. - ʋ 1-2. - P. 217 223.