КРИСТАЛЛИЧЕСКИЕ И МОЛЕКУЛЯРНЫЕ СТРУКТУРЫ АДДУКТОВ

ȼȿɋɌɇ. ɆɈɋɄ. ɍɇ-ɌȺ. ɋȿɊ. 2. ɏɂɆɂə. 2007. Ɍ. 48. ʋ 2
130
ɍȾɄ 541.44:546.623:546.828
lrjstbmmjygsljg j npmglumro}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:
b.bulychev@highp.chem.msu.ru)
.
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.