ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 2 130 ɍȾɄ 541.44:546.623:546.828 lrjstbmmjygsljg j npmglumro}g strultur} bffultpd (Cp2YCl)2.L (L = 2tev, fn, 1,4-fjplsbo) b.j. s¾½Ä¸, t.n. i¸ÉÀĸ¶, i.b. sȶƾÀĸ¶, c.n. cÉÁÑÍ»¸ (À¶Ê»ºÆ¶ ˾¾ͻÇÀÄ¿ È»ËÃÄÁĹ¾¾ ¾ ÃĸÑË Â¶È»Æ¾¶Áĸ; e-mail: [email protected]) . μ -Cl)]2. s¾ÃÈ»½¾Æĸ¶ÃÑ ¾ ¾½ÉÍ»ÃÑ Â»ÈĺÄ rsÈb ¶ººÉÀÈÑ [Cp2Y(μ μ -Cl)]2 2tev (5), {[Cp2Y(μ μ -Cl)(Cl)YCp2 (7). d ¶ººÉÀÈ» 5 Êƶ¹Â»ÃÈ (Cp2YCl)2 ÀÄÄƺ¾Ã¾1,4-º¾ÄÀǶÃ}n (6) ¾ Cp2Y(fn)(μ ÆÉ»È º¸» ÂÄÁ»ÀÉÁÑ tev (dY-O = 2.478 Å), ¶ ¸ 6 º¾Â»ÆÑ (Cp2YCl)2 Ǹµ½¶ÃÑ 1,4-º¾ÄÀǶÃÄ ¸ ÅÄÁ¾Â»ÆÃÉÔ Ì»ÅÒ (dY-O = 2,601 Å). d ¶ººÉÀÈ» 7, ÅÄÇÈÆÄ»ÃÃÄ ¶Ç¾Â»ÈƾÍÃÄ, ÂÄÁ»ÀÉÁ¶ fn Ǹµ½¶Ã¶ ķľ¾ ¶ÈĶ¾ O Ç ÄºÃ¾Â ¶ÈÄÂÄ Y (dY-O = 2,382; 2,448 Å), ĺ¾Ã ¶ÈÄ Cl µ¸Áµ»Èǵ ÂÄÇȾÀĸÑÂ, ¶ ¸ÈÄÆÄ¿ ¶ÈÄ Cl öËĺ¾Èǵ ¸ ÀÄÃÌ»¸Ä ÅÄÁļ»Ã¾¾. Ɇɟɬɚɥɥɨɰɟɧɨɜɵɟ ɩɪɨɢɡɜɨɞɧɵɟ ɊɁɗ ɢ Y ɩɪɨɹɜɥɹɸɬ ɫɜɨɣɫɬɜɚ ɤɢɫɥɨɬ Ʌɶɸɢɫɚ ɢ ɥɟɝɤɨ ɞɚɸɬ ɚɞɞɭɤɬɵ ɫ ɫɨɞɟɪɠɚɳɢɦɢ ɚɬɨɦ ɤɢɫɥɨɪɨɞɚ ɞɨɧɨɪɧɵɦɢ ɥɢɝɚɧɞɚɦɢ. Cɬɪɨɟɧɢɟ ɷɬɢɯ ɚɞɞɭɤɬɨɜ ɜɨ ɦɧɨɝɨɦ ɨɩɪɟɞɟɥɹɟɬɫɹ ɫɬɟɪɢɱɟɫɤɢɦɢ ɫɜɨɣɫɬɜɚɦɢ ɦɟɬɚɥɥɨɰɟɧɨɜɨɝɨ ɮɪɚɝɦɟɧɬɚ, ɧɨ ɬɚɤɠɟ ɡɚɜɢɫɢɬ ɢ ɨɬ ɬɢɩɚ O-ɥɢɝɚɧɞɚ (L) [1]. ɇɚɩɪɢɦɟɪ, ɞɢɦɟɪɧɵɣ ɯɥɨɪɢɞ Y ɫ ɨɛɴɟɦɧɵɦɢ C5Me5-ɝɪɭɩɩɚɦɢ (C5Me5) 2Y (μ-Cl)YCl(C5Me5) 2 (1) ɩɪɢ ɞɟɣɫɬɜɢɢ L ɞɢɫɫɨɰɢɢɪɭɟɬ ɧɚ ɦɨɧɨɹɞɟɪɧɵɟ ɚɞɞɭɤɬɵ ( C5Me5) 2YCl.L n , ɝɞɟ ɱɢɫɥɨ n ɜɚɪɶɢɪɭɟɬɫɹ ɜ ɡɚɜɢɫɢɦɨɫɬɢ ɨɬ ɫɬɪɨɟɧɢɹ L [1]. ȼ ɨɬɥɢɱɢɟ ɨɬ 1, ɤɨɦɩɥɟɤɫɵ ɫ ɧɟɡɚɦɟɳɟɧɧɵɦɢ C5H 5-ɝɪɭɩɩɚɦɢ ɧɟ ɞɢɫɫɨɰɢɢɪɭɸɬ ɩɪɢ ɞɟɣɫɬɜɢɢ ɬɚɤɢɯ L , ɤɚɤ ɌȽɎ, ɚ ɨɛɪɚɡɭɸɬ ɞɢɦɟɪɧɵɟ ɚɞɞɭɤɬɵ, ɧɚɩɪɢɦɟɪ, [(Cp2Ln(μ-Cl)]2.L 2 (Cp = C5H 5; Ln = Nd (2) [2], Er (3) [3]). ɉɨɥɚɝɚɹ, ɱɬɨ ɢɡɦɟɧɟɧɢɟ ɬɢɩɚ L ɦɨɠɟɬ ɫɭɳɟɫɬɜɟɧɧɨ ɜɥɢɹɬɶ ɧɚ ɫɜɹɡɵɜɚɧɢɟ ɜ ɤɨɦɩɥɟɤɫɚɯ ɫ ɧɟɡɚɦɟɳɟɧɧɵɦɢ Cp-ɝɪɭɩɩɚɦɢ, ɦɵ ɫɢɧɬɟɡɢɪɨɜɚɥɢ ɢ ɢɡɭɱɢɥɢ ɚɞɞɭɤɬɵ ɞɢɦɟɪɚ [(Cp2Y (μ-Cl)]2 (4) ɫ ɪɚɡɥɢɱɧɵɦɢ L. Ɂɞɟɫɶ ɦɵ ɩɪɢɜɨɞɢɦ ɞɚɧɧɵɟ ɨ ɬɪɟɯ ɬɚɤɢɯ ɚɞɞɭɤɬɚɯ: Ɋɢɫ. 1. ɋɬɪɭɤɬɭɪɚ ɚɞɞɭɤɬɚ 5. Ɉɫɧɨɜɧɵɟ ɫɜɹɡɢ (Å) ɢ ɭɝɥɵ (ɝɪɚɞ): Y(1)–Cl(1) 2,661(1); Y(1)–Cl(2) 2,810(1); Y(1)–O(1) 2,478(2); Y(1)–Cp(1) 2,382(2); Y(1)–Cp(2) 2,389(2); Y(2)–Cl(1) 2,793(1); . .. Y(2)–O(2) 2,452(2); Y ( 1 ) Y(2) 4,418(1); Cl(1)–Y(1)–Cl(2) 72,71(2); Cl(1)–Y(1)–O(1) 75,97(6); Cp(1)–Y(1)–Cp(2) 127,5; Y(1)–Cl(1)–Y(2) 108,19(3) (Cp2YCl)2.( C4H 8O )2 (5), [(Cp2YCl)2.C4H 8O2] n (6) ɢ Cp2Y(C4H 10O2) (μ-Cl)(Cl)YCp2 (7), ɩɨɥɭɱɟɧɧɵɯ ɢɡ 4 ɞɟɣɫɬɜɢɟɦ ɌȽɎ, 1,4 – ɞɢɨɤɫɚɧɚ ɢ 1,2-ɞɢɦɟɬɨɤɫɢɷɬɚɧɚ (ȾɆɗ) ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. p·Çɼº»Ã¾» Æ»½ÉÁÒȶÈĸ ɂɡɜɟɫɬɧɨ, ɱɬɨ ɜ ɞɢɦɟɪɧɨɦ ɤɨɦɩɥɟɤɫɟ 4 [4] ɤɚɠɞɵɣ ɚɬɨɦ Y (d0- ɫɨɫɬɨɹɧɢɟ) ɢɦɟɟɬ ɜɚɤɚɧɬɧɭɸ ɨɪɛɢɬɚɥɶ ɢ ɫɩɨɫɨɛɟɧ ɤɨɨɪɞɢɧɢɪɨɜɚɬɶ ɟɳɟ ɨɞɢɧ ɥɢɝɚɧɞ [5]. ȼ ɫɨɨɬɜɟɬɫɬɜɢɢ ɫ ɷɬɢɦ, ɪɟɚɤɰɢɹ 4 ɫ ɌȽɎ ɩɪɢɜɨɞɢɬ ɤ ɚɞɞɭɤɬɭ 5 (ɪɢɫ. 1), ɜ ɤɨɬɨɪɨɦ ɫɜɹɡɶ Y(μ-Cl)2Y ɫɨɯɪɚɧɹɟɬɫɹ, ɚ ɚɬɨɦɵ Y ɫɜɹɡɵɜɚɸɬ ɩɨ ɦɨɥɟɤɭɥɟ ɌȽɎ ɢ, ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɮɨɪɦɚɥɶɧɨ ɞɨɫɬɢɝɚɸɬ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɧɚɫɵɳɟɧɢɹ ɫ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɦ ɱɢɫɥɨɦ (ɤ.ɱ.), ɪɚɜɧɵɦ 9. ɋɬɪɭɤɬɭɪɚ ɚɞɞɭɤɬɚ 5 ɩɨɜɬɨɪɹɟɬ ɫɬɪɭɤɬɭɪɵ ɚɞɞɭɤɬɨɜ 2 ɢ 3, ɩɪɢɱɟɦ ɦɧɨɝɢɟ ɫɬɪɭɤɬɭɪɧɵɟ ɩɚɪɚɦɟɬɪɵ (ɧɚɩɪɢɦɟɪ, Cl–Er–Cl 72,2°; Er–Cl 2,666; 2,797 Å; Er–O 2,490 Å; Er…Er 4,42 Å [3]) ɜɟɫɶɦɚ ɛɥɢɡɤɢ ɩɚɪɚɦɟɬɪɚɦ 5. ȼ ɚɞɞɭɤɬɟ 6, ɩɨɥɭɱɟɧɧɨɦ ɩɪɢ ɪɟɚɤɰɢɢ 4 ɫ 1,4-ɞɢɨɤɫɚɧɨɦ, ɧɚɛɥɸɞɚɟɬɫɹ ɜ ɰɟɥɨɦ ɬɨɬ ɠɟ ɬɢɩ ɫɜɹɡɵɜɚɧɢɹ, ɱɬɨ ɢ ɜ 5. Ʉɚɠɞɵɣ ɚɬɨɦ Y ɜ 6, ɩɨɦɢɦɨ ɋɪ-ɥɢɝɚɧɞɨɜ, ɤɨɨɪɞɢɧɢɪɭɟɬ ɞɜɚ ɚɬɨɦɚ Cl ɢ ɚɬɨɦ O, ɥɟɠɚɳɢɟ ɜ ɛɢɫɫɟɤɬɨɪɧɨɣ ɩɥɨɫɤɨɫɬɢ ɮɪɚɝɦɟɧɬɚ Cp2Y (ɪɢɫ. 2). Ⱦɢɦɟɪɵ (Cp2YCl)2 ɜ 6 ɫɜɹɡɚɧɵ ɜ ɰɟɩɶ ɦɨɥɟɤɭɥɚɦɢ 1,4-ɞɢɨɤɫɚɧɚ, ɤɨɬɨɪɵɟ, ɧɚɯɨɞɹɫɶ ɜ ɤɨɧɮɨɪɦɚɰɢɢ “ɤɪɟɫɥɨ”, ɜɵɫɬɭɩɚɸɬ ɜ ɤɚɱɟɫɬɜɟ ɛɢɞɟɧɬɚɬɧɨɝɨ ɧɟɯɟɥɚɬɢɪɭɸɳɟɝɨ ɥɢɝɚɧɞɚ. ɋɪɚɜɧɟɧɢɟ ɫɬɪɭɤɬɭɪ 5 ɢ 6 ɩɨɤɚɡɵɜɚɟɬ, ɱɬɨ ɪɚɫɫɬɨɹɧɢɟ d( Y…Y) ɞɥɹ 5 (4,418 Å) ɧɚ 0,04 Å ɛɨɥɶɲɟ, ɱɟɦ ɞɥɹ 6 (4,376 Å) (ɜ ɤɨɦɩɥɟɤɫɟ 4 d( Y…Y) = 4,069 Å [4]). ɇɚɩɪɨɬɢɜ, d(Y–O) ɜ 5 (2,478 Å) ɧɚ 0,12 Å ɦɟɧɶɲɟ, ɱɟɦ ɜ 6 (2,601 Å). ɗɬɨ ɭɤɚɡɵɜɚɟɬ ɧɚ ɛɨɥɶɲɭɸ ɩɪɨɱɧɨɫɬɶ ɫɜɹɡɢ Y–ɌȽɎ ɢ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɛɨɥɟɟ ɜɵɫɨɤɢɦ ɜ ɫɪɚɜɧɟɧɢɢ ɫ 1,4-ɞɢɨɤɫɚɧɨɦ ɞɨɧɨɪɧɵɦ ɫɜɨɣɫɬɜɚɦ ɌȽɎ [1]. ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 2 131 ɋɯɟɦɚ Cl Y Cl 1 Ɋɢɫ. 2. ɋɬɪɭɤɬɭɪɚ ɮɪɚɝɦɟɧɬɚ ɩɨɥɢɦɟɪɧɨɣ ɰɟɩɢ ɚɞɞɭɤɬɚ 6. Ɉɫɧɨɜɧɵɟ ɫɜɹɡɢ (Å) ɢ ɭɝɥɵ (ɝɪɚɞ): Y(1)–Cl(1) 2,693(1); Y(1)–Cl(1b) 2,789(1); Y(1)–O(1) 2,601(2); Y(1)–Cp(1) 2,368(2); Y(1)–Cp(2) . .. 2,402(2); Y ( 1 ) Y(1b) 4,376(1); Cl(1)–Y(1)–Cl(1b) 74,08(2); Cl(1)– Y(1)–O(1) 71,72(4); Cl(1b)–Y(1)–O(1) 145,21(4); Cp(1)–Y(1)–Cp(2) 126,6; Y(1)–Cl(1)–Y(1b) 106,00(2) ɉɪɨɞɭɤɬ ɪɟɚɤɰɢɢ 4 ɫ ȾɆɗ (ɚɞɞɭɤɬ 7), ɜ ɨɬɥɢɱɢɟ ɨɬ ɫɨɟɞɢɧɟɧɢɣ 5 ɢ 6, ɢɦɟɟɬ ɧɟɨɛɵɱɧɨɟ ɚɫɢɦɦɟɬɪɢɱɧɨɟ ɫɬɪɨɟɧɢɟ (ɪɢɫ. 3). Ɂɞɟɫɶ ɦɨɥɟɤɭɥɚ ȾɆɗ ɤɨɨɪɞɢɧɢɪɨɜɚɧɚ ɨɛɨɢɦɢ ɚɬɨɦɚɦɢ O ɤ ɚɬɨɦɭ Y(1) (d(O–Y) = 2,382; 2,448 Å), ɱɬɨ ɩɪɢɜɨɞɢɬ ɤ ɪɚɡɪɵɜɭ ɨɞɧɨɣ ɢɡ ɦɨɫɬɢɤɨɜɵɯ ɫɜɹɡɟɣ Y(μ-Cl)2Y ɫ ɜɵɬɟɫɧɟɧɢɟɦ ɚɬɨɦɚ Cl ɜ ɤɨɧɰɟɜɨɟ ɩɨɥɨɠɟɧɢɟ ɤ ɚɬɨɦɭ Y(2). Ɉɱɟɜɢɞɧɨ, ɱɬɨ ɩɟɪɟɪɚɫɩɪɟɞɟɥɟɧɢɟ ɫɜɹɡɟɣ ɜ 7 ɨɛɭɫɥɨɜɥɟɧɨ ɩɪɨɱɧɵɦ ɯɟɥɚɬɧɵɦ ɫɜɹɡɵɜɚɧɢɟɦ ȾɆɗ-ɢɬɬɪɢɣ, ɤɨɬɨɪɨɟ ɞɥɹ ȾɆɗ, ɜ ɨɬɥɢɱɢɟ ɨɬ 1,4-ɞɢɨɤɫɚɧɚ, ɥɟɝɤɨ ɪɟɚɥɢɡɭɟɬɫɹ [6]. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɧɟɷɤɜɢɜɚɥɟɧɬɧɨɫɬɶ ɚɬɨɦɨɜ ɦɟɬɚɥɥɚ ɤɪɚɣɧɟ ɪɟɞɤɨ ɜɫɬɪɟɱɚɟɬɫɹ ɜ ɞɢɦɟɪɧɵɯ ɦɟɬɚɥɥɨɰɟɧɚɯ ɢ ɩɨ ɷɬɨɦɭ ɩɪɢɡɧɚɤɭ ɚɞɞɭɤɬ 7 ɫɯɨɞɟɧ ɫ Ɋɢɫ. 3. ɋɬɪɭɤɬɭɪɚ ɚɞɞɭɤɬɚ 7. Ɉɫɧɨɜɧɵɟ ɫɜɹɡɢ (Å) ɢ ɭɝɥɵ (ɝɪɚɞ): Y(1)-O(2) 2.382(3); Y(1)-O(1) 2.448(3); Y(1)-Cl(1) 2.785(1); Y(2)Cl(1) 2.657(1); Y(2)-Cl(2) 2.575(1); Y(1)-Cp(1) 2.37; Y(1)-Cp(2) … 2.38; Y(2)-Cp(1) 2.36; Y(2)-Cp(2) 2.36; Y(1) Y(2) 5.038(1); O(2)Y(1)-O(1) 65.77(1); Cl(2)-Y(2)-Cl(1) 98.10(3); Y(2)-Cl(1)-Y(1) 135.50(5); Cp(1)-Y(1)-Cp(2) 129.3; Cp(3)-Y(2)-Cp(4) 129.0 O O Cl Y Y Cl Y I 7 ɤɨɦɩɥɟɤɫɨɦ 1 [1, 7] (ɫɯɟɦɚ). Ɉɞɧɚɤɨ ɟɫɥɢ ɜ 1 ɨɛɚ ɚɬɨɦɚ Y ɤɨɨɪɞɢɧɚɰɢɨɧɧɨ ɧɟɧɚɫɵɳɟɧɵ (ɤ.ɱ. ɫɨɫɬɚɜɥɹɟɬ 7 ɢ 8) (ɥɢɝɚɧɞ C5Me5, ɤɚɤ ɢ C5H 5, ɡɚɧɢɦɚɟɬ ɬɪɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɦɟɫɬɚ [1]), ɬɨ ɜ 7 ɨɞɢɧ ɢɡ ɦɟɬɚɥɥɨɜ ɞɨɫɬɢɝɚɟɬ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɧɚɫɵɳɟɧɢɹ (ɤ.ɱ. ɫɨɫɬɚɜɥɹɟɬ 8 ɢ 9). ȼɟɪɨɹɬɧɨ, ɷɬɢɦ, ɚ ɬɚɤɠɟ ɛɨɥɶɲɢɦ ɫɬɟɪɢɱɟɫɤɢɦ ɧɚɩɪɹɠɟɧɢɟɦ ɜ 1 (d( Y…Y) ɜ 1 ɪɚɜɧɨ 5,354 Å, ɚ ɜ 7 – 5,038 Å) ɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɧɚɛɥɸɞɚɟɦɨɟ ɪɚɡɥɢɱɢɟ ɜ ɚɤɬɢɜɧɨɫɬɢ 1 ɢ 7 ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ Ɉ-ɥɢɝɚɧɞɚɦ. Ɍɚɤ, ɤɨɦɩɥɟɤɫ 1, ɤɚɤ ɭɠɟ ɭɩɨɦɢɧɚɥɨɫɶ ɜɵɲɟ, ɥɟɝɤɨ ɞɢɫɫɨɰɢɢɪɭɟɬ ɩɪɢ ɞɟɣɫɬɜɢɢ O-ɥɢɝɚɧɞɨɜ [1]. ȼ ɨɬɥɢɱɢɟ ɨɬ ɷɬɨɝɨ, ɚɞɞɭɤɬ 7, ɨɛɪɚɡɭɸɳɢɣɫɹ ɜ ɢɡɛɵɬɤɟ ȾɆɗ, ɧɟ ɩɪɟɬɟɪɩɟɜɚɟɬ ɞɚɥɶɧɟɣɲɟɝɨ ɪɚɫɳɟɩɥɟɧɢɹ ɞɨ ɞɜɭɯ ɦɨɧɨɹɞɟɪɧɵɯ ɦɨɥɟɤɭɥ Cp2Y(ȾɆɗ)Cl, ɱɟɝɨ ɦɨɠɧɨ ɛɵɥɨ ɨɠɢɞɚɬɶ, ɩɪɢɧɢɦɚɹ ɜɨ ɜɧɢɦɚɧɢɟ ɜɵɫɨɤɭɸ ɩɪɨɱɧɨɫɬɶ ɯɟɥɚɬɧɵɯ ɫɜɹɡɟɣ ɦɟɬɚɥɥ-ȾɆɗ. ÀÇŻƾ»ÃȶÁÒöµ ͶÇÈÒ ȼɫɟ ɨɩɟɪɚɰɢɢ ɩɪɨɜɨɞɢɥɢ ɜ ɚɬɦɨɫɮɟɪɟ ɚɪɝɨɧɚ ɢɥɢ ɜ ɜɚɤɭɭɦɟ. Ɋɚɫɬɜɨɪɢɬɟɥɢ ɨɱɢɳɚɥɢ ɩɟɪɟɝɨɧɤɨɣ ɛɟɧɡɨɮɟɧɨɧɤɟɬɢɥɨɦ ɧɚɬɪɢɹ, (Cp2YCl)2 ɩɨɥɭɱɚɥɢ ɩɨ ɢɡɜɟɫɬɧɨɣ ɦɟɬɨɞɢɤɟ [8], 1H-əɆɊ-ɫɩɟɤɬɪɵ ɡɚɩɢɫɵɜɚɥɢ ɧɚ ɩɪɢɛɨɪɟ “Bruker DPX300”. bººÉÀÈ 5. (Cp2YCl)2 (0,2 ɝ) ɪɚɫɬɜɨɪɢɥɢ ɜ ɫɦɟɫɢ ɬɨɥɭɨɥɚ (22 ɦɥ) ɢ ɌȽɎ (3 ɦɥ) ɩɪɢ 20°ɋ, ɪɚɫɬɜɨɪ ɭɩɚɪɢɥɢ ɞɨ ~1/3 ɧɚɱɚɥɶɧɨɝɨ ɨɛɴɟɦɚ ɢ ɨɫɬɚɜɢɥɢ ɧɚ ɧɨɱɶ ɩɪɢ 18°ɋ. ɉɨɥɭɱɟɧɧɵɟ ɛɟɫɰɜɟɬɧɵɟ ɤɪɢɫɬɚɥɥɵ (0,07 ɝ) ɨɬɞɟɥɢɥɢ, ɩɪɨɦɵɥɢ ɬɨɥɭɨɥɨɦ (1 ɦɥ) ɢ ɜɵɫɭɲɢɥɢ ɜ ɜɚɤɭɭɦɟ. ɇɚɣɞɟɧɨ (%): Cl (10,30); Y (26,85). C28H 36Cl2O2Y2. ȼɵɱɢɫɥɟɧɨ (%): Cl (10,85); Y (27,22). 1 H-əɆɊ, 300 MHz, (C6D 6, 20°C, δ (ɦ.ɞ.): 6.19 (ɫ, 10H, Cp); 3.45 (ɭɲ.ɫ, 4H, CH2O); 1.27 (ɭɲ.ɫ, 4H, C 2H 4). Ɉɞɢɧ ɤɪɢɫɬɚɥɥ ɛɵɥ ɨɬɨɛɪɚɧ ɞɥɹ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ. bººÉÀÈ 6. (Cp2YCl)2 (0,27ɝ) ɪɚɫɬɜɨɪɢɥɢ ɜ ɬɟɩɥɨɣ (45°ɋ) ɫɦɟɫɢ ɬɨɥɭɨɥɚ (35 ɦɥ) ɢ 1,4-ɞɢɨɤɫɚɧɚ (6 ɦɥ), ɪɚɫɬɜɨɪɭ ɩɨɡɜɨɥɢɥɢ ɦɟɞɥɟɧɧɨ (ɜ ɬɟɱɟɧɢɟ 24 ɱ) ɨɫɬɵɬɶ ɧɚ ɜɨɞɹɧɨɣ ɛɚɧɟ ɞɨ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ. ɉɨɥɭɱɟɧɧɵɟ ɛɟɫɰɜɟɬɧɵɟ ɤɪɢɫɬɚɥɥɵ (0,11 ɝ) ɨɬɞɟɥɢɥɢ ɨɬ ɦɚɬɨɱɧɨɝɨ ɪɚɫɬɜɨɪɚ, ɩɪɨɦɵɥɢ ɬɨɥɭɨɥɨɦ (1 ɦɥ) ɢ ɜɵɫɭɲɢɥɢ ɜ ɜɚɤɭɭɦɟ. ɇɚɣɞɟɧɨ (%): Cl (11,31); Y (29,44). C24H 28Cl2O2Y2. ȼɵɱɢɫɥɟɧɨ (%): Cl (11,89); Y ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 2 132 uÇÁĸ¾µ ÓÀÇŻƾ»Ãȶ ¾ ÀƾÇȶÁÁĹƶʾͻÇÀ¾» ˶ƶÀȻƾÇȾÀ¾ ¶ººÉÀÈĸ 5, 6 ¾ 7 Ⱥɞɞɭɤɬ 5 6 7 Ȼɪɭɬɬɨ–ɮɨɪɦɭɥɚ C28H36Cl2O2Y2 C24H28Cl2O2Y2 C24H30Cl2O2Y2 M 653,28 597,18 599,20 Ɋɚɡɦɟɪ ɤɪɢɫɬɚɥɥɚ/ɦɦ 0,30×0,40×0,55 0,20×0,30×0,40 0,25×0,30×0,35 Ɋɟɲɟɬɤɚ Ɇɨɧɨɤɥɢɧɧɚɹ Ɍɪɢɤɥɢɧɧɚɹ Ɉɪɬɨɪɨɦɛɢɱɟɫɤɚɹ ɉɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ P2(1)/c P-1 P2(1)2(1)2(1) a/Å 15,549(2) 8,175(1) 11,6501(15) b/Å 21,263(2), 8,201(1) 13,6572(16) c/Å 8,4090(9) 10,346(1) 15,455(2) α/ɝɪɚɞ 90 89,003(2) 90 β/ɝɪɚɞ 102,651(2) 73,059(2) 90 γ/ɝɪɚɞ 90 60,284(2) 90 V/Å3 2712,7(5) 569,49(10) 2459,0(5) Z 4 1 4 D/ɝ,ɫɦ–3 1,600 1,741 1,619 ɂɧɬɟɪɜɚɥ Q/ɝɪɚɞ 1,65–27,00 3,82–29,00 1,99–29,00 ɑɢɫɥɨ ɨɬɪɚɠɟɧɢɣ 5879 (2758) 20218 (5783) 21811 (6525) ɉɨɝɥɨɳɟɧɢɟ, μ, ɦɦ–1 5,323 4,478 4,931 R1 0,0720 0,0300 0,0827 wR2 [I >2s(I)] 0,0654 0,0540 0,0721 ɝɪɭɩɩɚ (ɧɟɡɚɜɢɫɢɦɵɯ) 29,81. 1H-əɆɊ, 300 MHz, C6D6, 20°C, δ (ɦ.ɞ.): 6.19 (ɫ, 20H, Cp); 3.36 (ɫ, 8H, ɞɢɨɤɫɚɧ). Ɉɞɢɧ ɤɪɢɫɬɚɥɥ ɛɵɥ ɨɬɨɛɪɚɧ ɞɥɹ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ. bººÉÀÈ 7 ɩɨɥɭɱɚɥɢ ɚɧɚɥɨɝɢɱɧɨ ɚɞɞɭɤɬɭ 5. ɂɡ (Cp2YCl)2 (0,2 ɝ) ɜ ɫɦɟɫɢ ɬɨɥɭɨɥɚ (25 ɦɥ) ɢ ȾɆɗ (2,5 ɦɥ) ɩɨɥɭɱɟɧɨ 0,06 ɝ ɛɟɫɰɜɟɬɧɵɯ ɤɪɢɫɬɚɥɥɨɜ. ɇɚɣɞɟɧɨ (%): Cl, 11.54; Y, 29.50. C24H 30Cl2O 2Y2. ȼɵɱɢɫɥɟɧɨ (%): Cl, 11.83; Y, 29.67. 1H-əɆɊ, 300 MHz, (C6D 5CD3, 20°C, δ (ɦ.ɞ.): 6.11 (ɫ, 20H, Cp); 3.24 (ɫ, 4H, CH2); 3.06 (ɫ, 6H, CH3). Ɉɞɢɧ ɤɪɢɫɬɚɥɥ ɛɵɥ ɨɬɨɛɪɚɧ ɞɥɹ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ. ɍɫɥɨɜɢɹ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ɦɨɧɨɤɪɢɫɬɚɥɥɨɜ 5, 6 ɢ 7, ɡɚɩɚɹɧɧɵɯ ɜ ɤɚɩɢɥɥɹɪɵ, ɢ ɤɪɢɫ- ɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɩɚɪɚɦɟɬɪɵ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥɢɰɟ. ɇɚɛɨɪɵ ɨɬɪɚɠɟɧɢɣ ɩɨɥɭɱɟɧɵ ɧɚ ɩɪɢɛɨɪɟ “Bruker SMART” ɩɪɢ 120 Ʉ, λ-Ɇɨ-Ʉα-ɢɡɥɭɱɟɧɢɟ. ɉɨɝɥɨɳɟɧɢɟ ɭɱɬɟɧɨ ɫ ɩɨɦɨɳɶɸ ɩɪɨɝɪɚɦɦɵ SADABS [9]. ɋɬɪɭɤɬɭɪɵ ɪɟɲɟɧɵ ɩɪɹɦɵɦ ɦɟɬɨɞɨɦ, ɧɟɜɨɞɨɪɨɞɧɵɟ ɚɬɨɦɵ ɥɨɤɚɥɢɡɨɜɚɧɵ ɜ ɪɚɡɧɨɫɬɧɵɯ ɫɢɧɬɟɡɚɯ ɢ ɭɬɨɱɧɟɧɵ ɩɨ F2hkl ɜ ɚɧɢɡɨɬɪɨɩɧɨɦ ɩɪɢɛɥɢɠɟɧɢɢ; ɚɬɨɦɵ ɜɨɞɨɪɨɞɚ ɩɨɦɟɳɟɧɵ ɜ ɝɟɨɦɟɬɪɢɱɟɫɤɢ ɪɚɫɫɱɢɬɚɧɧɵɟ ɩɨɡɢɰɢɢ ɢ ɭɱɬɟɧɵ ɩɪɢ ɭɬɨɱɧɟɧɢɢ ɜ ɦɨɞɟɥɢ “ɧɚɟɡɞɧɢɤɚ” ɫ U(H) = nU(C), ɝɞɟ U(C) – ɷɤɜɢɜɚɥɟɧɬɧɵɣ ɬɟɦɩɟɪɚɬɭɪɧɵɣ ɮɚɤɬɨɪ ɚɬɨɦɚ ɭɝɥɟɪɨɞɚ, ɫ ɤɨɬɨɪɵɦ ɫɜɹɡɚɧ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɣ ɚɬɨɦ ɇ, n = 1,2 ɢ 1,5 ɞɥɹ sp2- ɢ sp3ɚɬɨɦɨɜ ɭɝɥɟɪɨɞɚ. ȼɫɟ ɪɚɫɱɟɬɵ ɩɪɨɜɟɞɟɧɵ ɩɨ ɤɨɦɩɥɟɤɫɭ ɩɪɨɝɪɚɦɦ SHELXTL PLUS 5 [10]. ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 2 Ʉɨɨɪɞɢɧɚɬɵ ɚɬɨɦɨɜ ɢ ɩɨɥɧɵɟ ɫɬɪɭɤɬɭɪɧɵɟ ɞɚɧɧɵɟ ɞɟɩɨɧɢɪɨɜɚɧɵ ɜ Ʉɟɦɛɪɢɞɠɫɤɨɦ ɛɚɧɤɟ ɫɬɪɭɤɬɭɪɧɵɯ 133 ɞɚɧɧɵɯ: CCDC ʋ 293793 ɞɥɹ 5, ʋ. 244037 ɞɥɹ 6 ɢ ʋ 293792 ɞɥɹ 7. ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ 1. Evans W.J., Fujimoto C. H., Johnston M.A., Ziller J.W. // Organometallics. 2002. 21. P. 1825. 2. Zhongsheng J., Yongsheng L., Wen-Oi C. // Sci.Sin., Ser.B (Engl.Ed.). 1987. 30. P. 1136. 3. Ji-Zhu J., Zhong-Sheng J., Wen-Oi C. // Jiegou Huaxue (J.Struct.Chem.). 1992. 11. P. 204 (CA. 1993. 118. 202466x). 4. mÄ·ÀĸÇÀ¾¿ .c., sÄÁĸ»¿Í¾À e.m., cÉÁÑÍ»¸ c.n., gÆÄÊ»»¸ b.c. // ɀ. ɫɬɪɭɤɬ. ɯɢɦ. 1984. 25. ɋ. 170. 5. Lauher J.M., Hoffman R. // J. Am. Chem. Soc. 1976. 98. P. 1729. 6. Baisch1 U., Dell Amico D.B., Calderazzo F. et al. // Inorg. Chim. Acta. 2004. 357. P. 1538. 7. Evans W.J., Rausch M.D., Hunter W.E. et al. // Organometallics. 1985. 4. P. 553. 8. Holton J., Lappert M.F., Ballard D.G.H. et al. // J. Chem. Soc. Dalton Trans. 1979. N 1. P. 45. 9. Sheldrick G.M. // SADABS. 1998. 2.01. Bruker/Siemens Area Detector Absorption Correction Program, Bruker AXS, Madison, Wisconsin, USA. 10. Sheldrick G.M. // SHELXTL. 1998. 5.10. Structure Determination Software Suite, Bruker AXS, Madison, Wisconsin, USA. ɉɨɫɬɭɩɢɥɚ ɜ ɪɟɞɚɤɰɢɸ 06.02.06 CRYSTAL AND MOLECULAR STRUCTURES OF THE ADDUCTS (Cp2YCl)2.L (L = 2THF, DME, 1,4-.DIOXANE) A.I. Sizov, T.M. Zvukova, Z.A. Starikova, B.M. Bulychev (Division of Chemical Technology and New Materials) The yttrium(III) adducts, (Cp2YCl)2. C4H8O (5), [(Cp2YCl)2. C4H8O2]n (6) and Cp2Y(C4H10O2)(μ μCl)(Cl)YCp2 (7) were prepared by reactions of (Cp2YCl)2 with corresponding O-bases and were characterized by X-ray crystallography. The complex 5 consists of (Cp2YCl)2 dimers bonded with two THF molecules (dY-O = 2.478 Å). In adduct 6 the (Cp2YCl)2 dimers are linked by 1,4-dioxane into a polymeric chain with long (dY-O = 2.601 Å) bonds. In the asymmetric adduct 7 the DME molecule is bonded with one Y atom by both oxygen atoms (dY-O = 2.382, 2.448 Å) and the single bridge Y-Cl-Y bond is only presented.