ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɍɨɦ 47, ʋ 6 ɇɨɹɛɪɶ – ɞɟɤɚɛɪɶ ɋ. 1123 – 1127

ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2006. Ɍɨɦ 47, ʋ 6
ɇɨɹɛɪɶ – ɞɟɤɚɛɪɶ
ɋ. 1123 – 1127
ɍȾɄ 547.442+546.562+546.81
ɋɌɊɍɄɌɍɊȺ ɂ ɋȼɈɃɋɌȼȺ ȽȿɌȿɊɈɄɈɆɉɅȿɄɋɇɕɏ ɋɈȿȾɂɇȿɇɂɃ ɇȺ ɈɋɇɈȼȿ
ȽȿɄɋȺɎɌɈɊȺɐȿɌɂɅȺɐȿɌɈɇȺɌȺ ɋȼɂɇɐȺ(II) ɂ E-ȾɂɄȿɌɈɇȺɌɈȼ ɆȿȾɂ(II)
” 2006 ɂ.Ⱥ. Ȼɚɣɞɢɧɚ, ȼ.ȼ. Ʉɪɢɫɸɤ*, ɉ.Ⱥ. ɋɬɚɛɧɢɤɨɜ
ɂɧɫɬɢɬɭɬ ɧɟɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɢɦ. Ⱥ.ȼ. ɇɢɤɨɥɚɟɜɚ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 29 ɞɟɤɚɛɪɹ 2005 ɝ.
ɉɪɨɜɟɞɟɧɨ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɟ ɢɫɫɥɟɞɨɜɚɧɢɟ ɤɪɢɫɬɚɥɥɨɜ ɝɟɬɟɪɨɦɟɬɚɥɥɢɱɟɫɤɢɯ ɤɨɦɩɥɟɤɫɨɜ ɧɚ ɨɫɧɨɜɟ ɝɟɤɫɚɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬɚ ɫɜɢɧɰɚ(II) ɢ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɞɢ(II). Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɞɥɹ Cu(aa)2˜Pb(hfa)2: a = 8,741(2), b = 12,124(2),
c = 13,741(3) Å, D = 89,70(3), E = 89,50(3), J = 75,06(3)q, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ P-1,
Z = 2, dɜɵɱ = 2,084 ɝ/cɦ3; ɞɥɹ Cu(hfa)2˜Pb(hfa)2: a = 9,334(2), b = 14,584(3), c = 23,102(5) Å,
E = 96,82(3)°, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ P21/c, Z = 4, dɜɵɱ = 2,338 ɝ/cɦ3. ɉɨɤɚɡɚɧɨ, ɱɬɨ ɨɫɧɨɜɧɵɦ ɫɬɪɭɤɬɭɪɧɵɦ ɦɨɬɢɜɨɦ ɞɚɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɹɜɥɹɸɬɫɹ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɟ ɩɨɥɢɦɟɪɵ ɜ ɜɢɞɟ ɰɟɩɨɱɟɤ ɢɡ ɱɟɪɟɞɭɸɳɢɯɫɹ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɨɜ. ɉɪɢɜɟɞɟɧɵ ɪɟɡɭɥɶɬɚɬɵ ɬɟɪɦɨɝɪɚɜɢɦɟɬɪɢɱɟɫɤɨɝɨ ɢɫɫɥɟɞɨɜɚɧɢɹ ɩɨɥɭɱɟɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɦɟɞɶ, ɫɜɢɧɟɰ, E-ɞɢɤɟɬɨɧɚɬɵ, ɝɟɬɟɪɨɦɟɬɚɥɥɢɱɟɫɤɢɟ ɤɨɦɩɥɟɤɫɵ,
ɬɟɪɦɢɱɟɫɤɢɣ ɚɧɚɥɢɡ.
ȼȼȿȾȿɇɂȿ
ȼ ɩɪɟɞɵɞɭɳɢɯ ɪɚɛɨɬɚɯ [ 1 — 4 ] ɩɨ ɢɫɫɥɟɞɨɜɚɧɢɸ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɵ Eɞɢɤɟɬɨɧɚɬɨɜ ɫɜɢɧɰɚ ɛɵɥɨ ɩɨɤɚɡɚɧɨ, ɱɬɨ ɦɨɥɟɤɭɥɵ ɞɚɧɧɵɯ ɯɟɥɚɬɨɜ ɢɦɟɸɬ ɧɟɩɥɨɫɤɨɟ ɫɬɪɨɟɧɢɟ.
ȼɥɢɹɧɢɟ ɧɟɩɨɞɟɥɟɧɧɨɣ ɩɚɪɵ ɷɥɟɤɬɪɨɧɨɜ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ ɩɪɢɜɨɞɢɬ ɤ ɬɚɤɨɦɭ ɪɚɫɩɨɥɨɠɟɧɢɸ
ɥɢɝɚɧɞɨɜ, ɱɬɨ, ɜ ɫɢɥɭ ɫɜɨɟɝɨ ɫɪɚɜɧɢɬɟɥɶɧɨ ɛɨɥɶɲɨɝɨ ɪɚɞɢɭɫɚ, ɰɟɧɬɪɚɥɶɧɵɣ ɚɬɨɦ ɨɤɚɡɵɜɚɟɬɫɹ ɧɟ
ɩɪɢɤɪɵɬɵɦ ɞɨɧɨɪɧɵɦɢ ɚɬɨɦɚɦɢ ɫɨ ɜɫɟɯ ɫɬɨɪɨɧ. ȼ ɪɟɡɭɥɶɬɚɬɟ ɬɚɤɨɝɨ ɫɬɪɨɟɧɢɹ ɜ ɤɪɢɫɬɚɥɥɟ ɩɪɨɢɫɯɨɞɢɬ ɞɨɩɨɥɧɟɧɢɟ Ʉɑ ɦɟɬɚɥɥɚ ɞɨ 7—8 ɩɭɬɟɦ ɤɨɨɪɞɢɧɚɰɢɢ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ ɢɥɢ ɮɬɨɪɚ ɫɨɫɟɞɧɢɯ ɦɨɥɟɤɭɥ. Ɍɚɤɢɦ ɫɩɨɫɨɛɨɦ ɩɪɨɢɫɯɨɞɢɬ ɨɛɪɚɡɨɜɚɧɢɟ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɩɨɥɢɦɟɪɨɜ ɜ ɜɢɞɟ
ɰɟɩɨɱɟɤ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɚ, ɭɩɚɤɨɜɤɚ ɤɨɬɨɪɵɯ ɢ ɨɛɪɚɡɭɟɬ ɤɪɢɫɬɚɥɥ. ɉɪɢ ɷɬɨɦ ɦɨɥɟɤɭɥɵ ɨɪɢɟɧɬɢɪɨɜɚɧɵ ɬɚɤ, ɱɬɨ ɞɢɩɨɥɶɧɵɣ ɦɨɦɟɧɬ ɩɨɥɭɱɚɟɬɫɹ ɜɡɚɢɦɧɨ ɫɤɨɦɩɟɧɫɢɪɨɜɚɧɧɵɦ.
Ȼɵɥɨ ɩɨɤɚɡɚɧɨ, ɱɬɨ ɫɬɟɩɟɧɶ ɚɫɫɨɰɢɚɰɢɢ ɜ ɰɟɩɨɱɤɚɯ ɦɨɥɟɤɭɥ ɡɚɜɢɫɢɬ ɨɬ ɬɢɩɚ ɡɚɦɟɫɬɢɬɟɥɹ ɜ
ɥɢɝɚɧɞɟ. ɇɚɩɪɢɦɟɪ, ɧɚɥɢɱɢɟ ɨɛɴɟɦɧɵɯ ɬɪɟɬ-ɛɭɬɢɥɶɧɵɯ ɡɚɦɟɫɬɢɬɟɥɟɣ ɜ ɞɢɩɢɜɚɥɨɢɥɦɟɬɚɧɚɬɟ
ɫɜɢɧɰɚ ɩɪɟɩɹɬɫɬɜɭɟɬ ɨɛɪɚɡɨɜɚɧɢɸ ɧɟ ɬɨɥɶɤɨ ɩɨɥɢɦɟɪɨɜ, ɧɨ ɢ ɞɢɦɟɪɨɜ. ȼ ɬɨ ɠɟ ɜɪɟɦɹ ɧɚɥɢɱɢɟ
ɮɬɨɪɢɪɨɜɚɧɧɵɯ ɡɚɦɟɫɬɢɬɟɥɟɣ ɩɪɢɜɨɞɢɬ ɤ ɭɜɟɥɢɱɟɧɢɸ ɚɤɰɟɩɬɨɪɧɵɯ ɫɜɨɣɫɬɜ ɚɬɨɦɚ ɦɟɬɚɥɥɚ ɢ,
ɤɚɤ ɫɥɟɞɫɬɜɢɟ, ɤ ɨɛɪɚɡɨɜɚɧɢɸ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɩɨɥɢɦɟɪɨɜ. Ɍɟɦ ɧɟ ɦɟɧɟɟ, ɷɬɢ ɤɨɦɩɥɟɤɫɵ ɩɪɢ
ɧɚɝɪɟɜɚɧɢɢ ɩɟɪɟɯɨɞɹɬ ɜ ɝɚɡɨɜɭɸ ɮɚɡɭ ɜ ɜɢɞɟ ɦɨɧɨɦɟɪɨɜ.
ȼ ɫɜɹɡɢ ɫ ɬɚɤɢɦ ɢɧɬɟɪɟɫɧɵɦ ɫɬɪɨɟɧɢɟɦ ɦɨɥɟɤɭɥ ɢ ɤɪɢɫɬɚɥɥɨɜ E-ɞɢɤɟɬɨɧɚɬɨɜ ɫɜɢɧɰɚ(II)
ɜɨɡɧɢɤɥɚ ɢɞɟɹ ɡɚɦɟɧɢɬɶ ɱɚɫɬɶ ɦɨɥɟɤɭɥ, ɧɚɩɪɢɦɟɪ ɜ Pb(hfa)2, ɧɚ ɦɨɥɟɤɭɥɵ ɤɨɦɩɥɟɤɫɨɜ ɞɪɭɝɨɝɨ
ɦɟɬɚɥɥɚ. ȼ ɤɚɱɟɫɬɜɟ ɬɚɤɨɜɵɯ ɛɵɥɢ ɜɵɛɪɚɧɵ ɨɞɧɨɬɢɩɧɵɟ E-ɞɢɤɟɬɨɧɚɬɵ ɦɟɞɢ(II). ɋɬɪɭɤɬɭɪɧɚɹ
ɯɢɦɢɹ ɞɚɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɦɟɞɢ ɯɨɪɨɲɨ ɨɩɢɫɚɧɚ ɜ ɨɛɡɨɪɟ [ 5 ], ɚ ɫɬɪɭɤɬɭɪɚ Pb(hfa)2 — ɜ [ 1, 4 ].
ȼ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ ɧɚɦɢ ɨɩɢɫɵɜɚɸɬɫɹ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɟ ɫɬɪɭɤɬɭɪɵ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɵɯ
ɫɨɟɞɢɧɟɧɢɣ ɫɨɫɬɚɜɚ Cu(aa)2˜Pb(hfa)2 ɢ Cu(hfa)2˜Pb(hfa)2, ɩɨɥɭɱɟɧɧɵɯ ɫɨɤɪɢɫɬɚɥɥɢɡɚɰɢɟɣ ɢɡ ɪɚɫ-
* E-mail: [email protected]
1124
ɂ.Ⱥ. ȻȺɃȾɂɇȺ, ȼ.ȼ. ɄɊɂɋɘɄ, ɉ.Ⱥ. ɋɌȺȻɇɂɄɈȼ
ɬɜɨɪɚ, ɝɞɟ ɚɚ = ɚɰɟɬɢɥɚɰɟɬɨɧɚɬ (ɩɟɧɬɚɧ-2,4-ɞɢɨɧ) ɢ hfa = ɝɟɤɫɚɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬ (1,1,1,5,5,5ɝɟɤɫɚɮɬɨɪɩɟɧɬɚɧ-2,4-ɞɢɨɧ).
ɗɄɋɉȿɊɂɆȿɇɌȺɅɖɇȺə ɑȺɋɌɖ
ɂɫɫɥɟɞɨɜɚɧɧɵɟ ɫɨɟɞɢɧɟɧɢɹ ɩɨɥɭɱɟɧɵ ɦɟɬɨɞɨɦ ɫɨɤɪɢɫɬɚɥɥɢɡɚɰɢɢ ɢɡ ɬɨɥɭɨɥɚ. Ⱦɥɹ ɷɬɨɝɨ
ɷɤɜɢɦɨɥɹɪɧɵɟ ɤɨɥɢɱɟɫɬɜɚ ɢɧɞɢɜɢɞɭɚɥɶɧɵɯ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɞɢ(II) ɢ ɫɜɢɧɰɚ(II) ɨɞɧɨɜɪɟɦɟɧɧɨ
ɪɚɫɬɜɨɪɹɥɢ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. ɉɪɢ ɦɟɞɥɟɧɧɨɦ ɢɫɩɚɪɟɧɢɢ ɪɚɫɬɜɨɪɢɬɟɥɹ ɜ ɚɬɦɨɫɮɟɪɟ
ɚɡɨɬɚ ɨɛɪɚɡɨɜɵɜɚɥɢɫɶ ɝɨɥɭɛɵɟ ɢɝɨɥɶɱɚɬɵɟ ɤɪɢɫɬɚɥɥɵ Cu(aa)2˜Pb(hfa)2 ɢ ɫɜɟɬɥɨ-ɡɟɥɟɧɵɟ ɤɪɢɫɬɚɥɥɵ Cu(hfa)2˜Pb(hfa)2 ɜ ɜɢɞɟ ɩɥɨɫɤɢɯ ɩɪɢɡɦ.
ɋɨɫɬɚɜ ɫɨɟɞɢɧɟɧɢɣ ɩɨɞɬɜɟɪɠɞɟɧ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɵɦ ɚɧɚɥɢɡɨɦ ɨɬɨɛɪɚɧɧɵɯ ɦɨɧɨɤɪɢɫɬɚɥɥɨɜ ɤɚɠɞɨɝɨ ɫɨɟɞɢɧɟɧɢɹ. ɂɯ ɩɪɟɞɫɬɚɜɢɦɨɫɬɶ ɩɨɞɬɜɟɪɠɞɟɧɚ ɊɎȺ ɩɨɪɨɲɤɨɝɪɚɦɦ. Ɋɟɧɬɝɟɧɨɝɪɚɮɢɱɟɫɤɨɟ ɢɫɫɥɟɞɨɜɚɧɢɟ (ȾɊɈɇ-3Ɇ, CuKD-ɢɡɥɭɱɟɧɢɟ, ɤɨɦɧɚɬɧɚɹ ɬɟɦɩɟɪɚɬɭɪɚ) ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨɛ ɨɞɧɨɮɚɡɧɨɫɬɢ ɩɨɥɭɱɟɧɧɨɝɨ ɩɪɨɞɭɤɬɚ. ɍɬɨɱɧɟɧɢɟ ɩɚɪɚɦɟɬɪɨɜ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɢ ɢ
ɩɨɥɭɱɟɧɢɟ ɧɚɛɨɪɚ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢɧɬɟɧɫɢɜɧɨɫɬɟɣ ɞɥɹ ɪɚɫɲɢɮɪɨɜɤɢ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ
ɫɬɪɭɤɬɭɪɵ ɩɪɨɜɨɞɢɥɢ ɧɚ ɚɜɬɨɦɚɬɢɱɟɫɤɨɦ ɞɢɮɪɚɤɬɨɦɟɬɪɟ CAD-4 (MoKD-ɢɡɥɭɱɟɧɢɟ, ɝɪɚɮɢɬɨɜɵɣ
ɦɨɧɨɯɪɨɦɚɬɨɪ, T/2T-ɫɤɚɧɢɪɨɜɚɧɢɟ). ɋɬɪɭɤɬɭɪɵ ɪɟɲɟɧɵ ɫɬɚɧɞɚɪɬɧɵɦ ɦɟɬɨɞɨɦ ɬɹɠɟɥɨɝɨ ɚɬɨɦɚ
ɢ ɭɬɨɱɧɟɧɵ ɜ ɚɧɢɡɨɬɪɨɩɧɨ-ɢɡɨɬɪɨɩɧɨɦ ɩɪɢɛɥɢɠɟɧɢɢ. Ɋɚɫɱɟɬɵ ɜɵɩɨɥɧɟɧɵ ɩɨ ɤɨɦɩɥɟɤɫɭ ɩɪɨɝɪɚɦɦ SHELX-97 [ 6 ]. Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɩɚɪɚɦɟɬɪɵ ɢ ɭɫɥɨɜɢɹ ɷɤɫɩɟɪɢɦɟɧɬɚ ɩɪɢɜɟɞɟɧɵ ɜ
ɬɚɛɥ. 1. Ⱦɨɩɨɥɧɢɬɟɥɶɧɵɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɞɨɫɬɭɩɧɵ ɢɡ Ʉɟɦɛɪɢɞɠɫɤɨɝɨ ɰɟɧɬɪɚ
ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɯ ɞɚɧɧɵɯ (http://www.ccdc.cam.ac.uk/): ɞɥɹ Pb(hfa)2 ʋ 286889, ɞɥɹ
Cu(aa)2˜Pb(hfa)2 ʋ 286968, ɞɥɹ Cu(hfa)2˜Pb(hfa)2 ʋ 286969.
Ɍɟɪɦɢɱɟɫɤɢɣ ɚɧɚɥɢɡ ɩɪɨɜɨɞɢɥɢ ɧɚ ɞɟɪɢɜɚɬɨɝɪɚɮɟ Q-1500-D (MOM, ȼɟɧɝɪɢɹ) ɜ ɚɬɦɨɫɮɟɪɟ
ɝɟɥɢɹ. ɋɤɨɪɨɫɬɶ ɧɚɝɪɟɜɚ ɛɵɥɚ 5q/ɦɢɧ, ɨɛɪɚɡɰɵ (a10 ɦɝ) ɩɨɦɟɳɚɥɢ ɜ ɨɬɤɪɵɬɵɟ ɤɜɚɪɰɟɜɵɟ ɬɢɝɥɢ.
Ɍɚɛɥɢɰɚ 1
Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɢ ɩɚɪɚɦɟɬɪɵ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ
ɉɚɪɚɦɟɬɪ
Cu(aa)2˜Pb(hfa)2
Cu(hfa)2˜Pb(hfa)2
ɋɬɟɯɢɨɦɟɬɪɢɱɟɫɤɚɹ ɮɨɪɦɭɥɚ
Ɇɨɥɟɤɭɥɹɪɧɵɣ ɜɟɫ
Ɍɟɦɩɟɪɚɬɭɪɚ, K
Ⱦɥɢɧɚ ɜɨɥɧɵ, Å
ɋɢɧɝɨɧɢɹ
ɉɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ
ɉɚɪɚɦɟɬɪɵ ɹɱɟɣɤɢ, Å, ɝɪɚɞ.
C20H16CuF12O8Pb
883,06
293(2)
0,71069
Ɍɪɢɤɥɢɧɧɚɹ
P-1
a = 8,741(2), D = 89,70(3),
b = 12,124(2), E = 89,50(3),
c = 13,741(3), J = 75,06(3)
1406,9(5)
2
2,084
6,852
838
ɨɬ 1,74 ɞɨ 22,49
3589 / 3334
[R(int) = 0,0229]
3334 / 0 / 384
R1 = 0,0310,
wR2 = 0,0464
R1 = 0,0535,
wR2 = 0,0499
C20H4CuF24O8Pb
1098,96
293(2)
0,71069
Ɇɨɧɨɤɥɢɧɧɚɹ
P21/c
a = 9,334(2), D = 90,
b = 14,584(3), E = 96,82(3),
c = 23,102(5), J = 90
3122,6(11)
4
2,338
6,252
2060
ɨɬ 1,78 ɞɨ 24,49
3385 / 3226
[R(int) = 0,0232]
3226 / 0 / 482
R1 = 0,0352,
wR2 = 0,0759
R1 = 0,0731,
wR2 = 0,0826
Ɉɛɴɟɦ, Å3
Z
ɉɥɨɬɧɨɫɬɶ (ɪɚɫɱɟɬɧɚɹ), ɝ/ɫɦ3
Ʉɨɷɮɮɢɰɢɟɧɬ ɩɨɝɥɨɳɟɧɢɹ, ɦɦ–1
F(000)
Ⱦɢɚɩɚɡɨɧ ɫɛɨɪɚ ɞɚɧɧɵɯ ɩɨ T, ɝɪɚɞ.
ɑɢɫɥɨ ɢɡɦɟɪ. / ɧɟɡɚɜɢɫ. ɪɟɮɥɟɤɫɨɜ
ɑɢɫɥɨ ɪɟɮɥɟɤɫɨɜ / ɨɝɪ. / ɩɚɪɚɦɟɬɪɨɜ
R-ɮɚɤɬɨɪ [I ! 2V(I )]
R-ɮɚɤɬɨɪ (ɜɫɟ ɞɚɧɧɵɟ)
ɄɊɂɋɌȺɅɅɂɑȿɋɄɂȿ ɋɌɊɍɄɌɍɊɕ Cu(aa)2˜Pb(hfa)2 ɂ Cu(hfa)˜Pb(hfa)2
1125
ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ
ɋɨɝɥɚɫɧɨ ɪɟɡɭɥɶɬɚɬɚɦ ɪɟɧɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɢɫɫɥɟɞɨɜɚɧɢɹ ɜɟɳɟɫɬɜɚ, ɩɨɥɭɱɟɧɧɵɟ ɫɨɤɪɢɫɬɚɥɥɢɡɚɰɢɟɣ, ɹɜɥɹɸɬɫɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɫɨɫɬɚɜɚ 1:1. ɉɪɢ ɷɬɨɦ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ ɩɪɨɜɟɪɟɧɨ, ɱɬɨ ɩɪɢ ɨɬɤɥɨɧɟɧɢɢ ɨɬ ɷɤɜɢɦɨɥɹɪɧɨɫɬɢ ɢɫɯɨɞɧɨɣ ɫɦɟɫɢ ɫɬɟɯɢɨɦɟɬɪɢɹ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɨɣ ɮɚɡɵ ɨɫɬɚɟɬɫɹ ɩɨɫɬɨɹɧɧɨɣ, ɚ ɢɡɛɵɬɨɱɧɵɣ ɤɨɦɩɨɧɟɧɬ ɤɪɢɫɬɚɥɥɢɡɭɟɬɫɹ ɨɬɞɟɥɶɧɨ.
ɉɨɤɚɡɚɧɨ ɬɚɤɠɟ, ɱɬɨ ɜ ɞɚɧɧɨɣ ɫɢɫɬɟɦɟ ɧɟ ɩɪɨɢɫɯɨɞɢɬ ɨɛɦɟɧɚ ɥɢɝɚɧɞɚɦɢ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ ɝɟɬɟɪɨɥɢɝɚɧɞɧɵɯ ɫɨɟɞɢɧɟɧɢɣ, ɱɬɨ ɯɚɪɚɤɬɟɪɧɨ, ɧɚɩɪɢɦɟɪ, ɞɥɹ ɬɟɯ ɠɟ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɞɢ(II) [ 7 ].
ȼ ɫɬɪɭɤɬɭɪɟ Cu(aa)2˜Pb(hfa)2 ɤɨɦɩɥɟɤɫɵ ɦɟɬɚɥɥɨɜ ɨɛɪɚɡɭɸɬ ɰɟɩɨɱɤɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɩɨɥɢɦɟɪɨɜ, ɜ ɤɨɬɨɪɵɯ ɦɨɥɟɤɭɥɵ ɱɟɪɟɞɭɸɬɫɹ ɜ ɪɟɝɭɥɹɪɧɨɦ ɩɨɪɹɞɤɟ ɜɞɨɥɶ ɨɫɢ Z. ɋɬɪɭɤɬɭɪɧɵɟ
ɟɞɢɧɢɰɵ — ɦɨɥɟɤɭɥɵ Cu(aa)2, ɡɚɧɢɦɚɸɳɢɟ ɰɟɧɬɪɨɫɢɦɦɟɬɪɢɱɧɵɟ ɩɨɡɢɰɢɢ, ɢ ɦɨɥɟɤɭɥɵ
Pb(hfa)2, ɧɚɯɨɞɹɳɢɟɫɹ ɜ ɨɛɳɟɦ ɩɨɥɨɠɟɧɢɢ (ɪɢɫ. 1). ɋɪɟɞɧɟɟ ɡɧɚɱɟɧɢɟ ɞɥɢɧ ɯɟɥɚɬɧɵɯ ɫɜɹɡɟɣ
Cu—O (ɬɚɛɥ. 2) ɩɨɱɬɢ ɫɨɜɩɚɞɚɟɬ ɫ ɚɧɚɥɨɝɢɱɧɵɦɢ ɜ ɫɬɪɭɤɬɭɪɟ ɢɧɞɢɜɢɞɭɚɥɶɧɨɝɨ Cu(aa)2 1,92 Å, ɚ
ɯɟɥɚɬɧɵɣ ɭɝɨɥ OCuO 93,6q ɧɟɫɤɨɥɶɤɨ ɦɟɧɶɲɟ ɜ ɫɪɚɜɧɟɧɢɢ ɫ 95q [ 83 ]. ɉɥɨɫɤɨɤɜɚɞɪɚɬɧɚɹ ɤɨɨɪɞɢɧɚɰɢɹ ɞɜɭɯ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢ ɧɟɡɚɜɢɫɢɦɵɯ ɚɬɨɦɨɜ ɦɟɞɢ ɞɨɩɨɥɧɹɟɬɫɹ ɞɨ ɜɵɬɹɧɭɬɨɝɨ ɨɤɬɚɷɞɪɚ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɫɨɫɟɞɧɢɯ ɤɨɦɩɥɟɤɫɨɜ ɫɜɢɧɰɚ ɫ ɪɚɫɫɬɨɹɧɢɹɦɢ Cu}O 2,75 ɢ 2,80 Å ɞɥɹ
Cu(1) ɢ Cu(2) ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. Ʉɨɨɪɞɢɧɚɰɢɹ ɚɬɨɦɨɜ ɫɜɢɧɰɚ (4+4) ɨɛɪɚɡɨɜɚɧɚ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɞɜɭɯ ɛɢɞɟɧɬɚɬɧɨ ɤɨɨɪɞɢɧɢɪɨɜɚɧɧɵɯ hfa-ɥɢɝɚɧɞɨɜ ɫ ɪɚɫɫɬɨɹɧɢɹɦɢ Pb—O 2,38—2,50 Å ɢ ɱɟɬɵɪɶɦɹ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɞɜɭɯ ɫɨɫɟɞɧɢɯ ɤɨɦɩɥɟɤɫɨɜ ɦɟɞɢ ɫ ɪɚɫɫɬɨɹɧɢɹɦɢ Pb—O 2,83—
2,96 Å. Ɋɚɫɫɬɨɹɧɢɹ Pb…Cu ɜ ɰɟɩɨɱɤɟ ɦɨɥɟɤɭɥ ɫɨɫɬɚɜɥɹɸɬ 3,63 Å, ɱɬɨ ɝɨɪɚɡɞɨ ɤɨɪɨɱɟ ɪɚɫɫɬɨɹɧɢɹ
Pb…Pb (4,3 Å) ɜ ɢɧɞɢɜɢɞɭɚɥɶɧɨɦ Pb(hfa)2 [ 4 ].
ɋɬɪɭɤɬɭɪɚ Cu(hfa)2˜Pb(hfa)2 ɩɨɫɬɪɨɟɧɚ ɬɚɤɠɟ ɢɡ ɰɟɩɨɱɟɤ ɱɟɪɟɞɭɸɳɢɯɫɹ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɨɜ ɜɞɨɥɶ ɨɫɢ Y. Ʉɨɦɩɥɟɤɫ ɫɜɢɧɰɚ ɧɚɯɨɞɢɬɫɹ ɜ ɨɛɳɟɦ ɩɨɥɨɠɟɧɢɢ, ɦɨɥɟɤɭɥɵ Cu(hfa)2 ɡɚɧɢɦɚɸɬ
ɞɜɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢ ɧɟɡɚɜɢɫɢɦɵɟ ɰɟɧɬɪɚɥɶɧɨ-ɫɢɦɦɟɬɪɢɱɧɵɟ ɩɨɡɢɰɢɢ (ɪɢɫ. 2). Ʉɨɨɪɞɢɧɚɰɢɨɧɧɨɟ ɨɤɪɭɠɟɧɢɟ ɚɬɨɦɚ ɫɜɢɧɰɚ ɨɛɪɚɡɨɜɚɧɨ ɱɟɬɵɪɶɦɹ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɞɜɭɯ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨ ɫɜɹɡɚɧɧɵɯ hfa-ɥɢɝɚɧɞɨɜ, ɩɪɢ ɷɬɨɦ ɜ ɞɨɩɨɥɧɢɬɟɥɶɧɨɣ ɤɨɨɪɞɢɧɚɰɢɢ ɚɬɨɦɚ ɫɜɢɧɰɚ ɭɱɚɫɬɜɭɸɬ ɱɟɬɵɪɟ ɚɬɨɦɚ ɤɢɫɥɨɪɨɞɚ ɫɨɫɟɞɧɢɯ ɤɨɦɩɥɟɤɫɨɜ ɦɟɞɢ ɫ ɛɨɥɶɲɢɦɢ ɦɨɫɬɢɤɨɜɵɦɢ ɪɚɫɫɬɨɹɧɢɹɦɢ Pb—O ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɩɪɟɞɵɞɭɳɟɣ ɫɬɪɭɤɬɭɪɨɣ. ɑɬɨ ɤɚɫɚɟɬɫɹ ɤɨɧɬɚɤɬɨɜ Pb—F, ɬɨ ɬɚɤɨɜɵɟ
ɧɚɛɥɸɞɚɸɬɫɹ ɫ ɭɱɚɫɬɢɟɦ ɚɬɨɦɨɜ ɮɬɨɪɚ, ɩɪɢɧɚɞɥɟɠɚɳɢɯ ɤɨɦɩɥɟɤɫɭ ɦɟɞɢ. ȼ ɰɟɩɨɱɤɚɯ
Cu(hfa)2˜Pb(hfa)2 ɭɠɟ ɧɟ ɧɚɛɥɸɞɚɟɬɫɹ ɬɚɤɚɹ ɪɟɝɭɥɹɪɧɨɫɬɶ ɞɥɹ ɤɨɦɩɥɟɤɫɨɜ ɦɟɞɢ, ɤɚɤ ɜ ɩɪɟɞɵɞɭɳɟɣ ɫɬɪɭɤɬɭɪɟ. Ⱥɬɨɦ ɦɟɞɢ ɬɚɤɠɟ ɞɨɩɨɥɧɹɟɬ ɩɥɨɫɤɨɤɜɚɞɪɚɬɧɭɸ ɤɨɨɪɞɢɧɚɰɢɸ ɞɨ ɨɤɬɚɷɞɪɢɱɟɫɤɨɣ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ ɫɨɫɟɞɧɢɯ ɤɨɦɩɥɟɤɫɨɜ ɫɜɢɧɰɚ. Ⱦɥɹ ɞɜɭɯ ɪɚɡɧɵɯ ɦɨɥɟɤɭɥ Cu(hfa)2 ɞɥɢɧɚ
ɫɜɹɡɟɣ Cu—O ɜ ɯɟɥɚɬɚɯ ɫɨɫɬɚɜɥɹɟɬ ɜ ɫɪɟɞɧɟɦ 1,87 ɢ 1,98 Å (ɫɦ. ɬɚɛɥ. 2). ɉɪɢ ɷɬɨɦ ɯɟɥɚɬɧɵɟ ɭɝɥɵ ɬɨɠɟ ɫɭɳɟɫɬɜɟɧɧɨ ɪɚɡɥɢɱɚɸɬɫɹ: 87,8 ɢ 98,1q ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ (ɞɥɹ ɫɪɚɜɧɟɧɢɹ: ɜ ɱɢɫɬɨɦ
Cu(hfa)2 ɦɨɥɟɤɭɥɵ ɯɟɥɚɬɚ ɧɟ ɹɜɥɹɸɬɫɹ ɰɟɧɬɪɚɥɶɧɨ-ɫɢɦɦɟɬɪɢɱɧɵɦɢ, ɢ ɯɟɥɚɬɧɵɟ ɭɝɥɵ ɜ ɦɨɥɟɤɭɥɟ ɫɨɫɬɚɜɥɹɸɬ 92,2 ɢ 93,7q [ 9 ]).
Ɋɢɫ. 1. Ɏɪɚɝɦɟɧɬ ɫɬɪɭɤɬɭɪɵ Cu(ɚɚ)2˜Pb(hfa)2
1126
ɂ.Ⱥ. ȻȺɃȾɂɇȺ, ȼ.ȼ. ɄɊɂɋɘɄ, ɉ.Ⱥ. ɋɌȺȻɇɂɄɈȼ
Ɍɚɛɥɢɰɚ 2
ȼ Cu(hfa)2˜Pb(hfa)2 ɞɨɩɨɥɧɢɬɟɥɶɧɚɹ ɤɨɨɪɞɢɧɚɰɢɹ
ɚɬɨɦɚ ɦɟɞɢ (4+2) ɨɛɪɚɡɨɜɚɧɚ ɚɬɨɦɚɦɢ ɤɢȼɵɛɪɚɧɧɵɟ ɞɥɢɧɵ ɫɜɹɡɟɣ d (Å) ɢ ɭɝɥɵ Z (ɝɪɚɞ.)
ɫɥɨɪɨɞɚ
ɫɨɫɟɞɧɢɯ Pb-ɤɨɦɩɥɟɤɫɨɜ. Ɉɞɧɚɤɨ ɧɚɞɥɹ ɩɨɥɭɱɟɧɧɵɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɵɯ ɫɨɟɞɢɧɟɧɢɣ
ɛɥɸɞɚɟɬɫɹ ɫɭɳɟɫɬɜɟɧɧɚɹ ɪɚɡɧɢɰɚ ɜ ɦɨɫɬɢɤɨɜɵɯ
Cu(ɚɚ)2˜Pb(hfa)2
Cu(hfa)2˜Pb(hfa)2
ɫɜɹɡɹɯ Cu—O: ɞɥɹ ɨɞɧɨɣ ɦɨɥɟɤɭɥɵ ɤɨɦɩɥɟɤɫɚ
ɋɜɹɡɶ
d
ɋɜɹɡɶ
d
ɦɟɞɢ ɷɬɨ ɪɚɫɫɬɨɹɧɢɟ ɹɜɥɹɟɬɫɹ ɫɪɚɜɧɢɬɟɥɶɧɨ ɤɨɪɨɬɤɢɦ, ɚ ɞɥɹ ɞɪɭɝɨɣ ɛɨɥɶɲɟ ɱɟɦ ɜ
Pb—O(5)
2,383(7) Pb—O(5) 2,412(7)
Cu(ɚɚ)
2˜Pb(hfa)2. Ʉɪɨɦɟ ɬɨɝɨ, ɨɱɟɜɢɞɧɨ, ɱɬɨ ɞɥɹ
Pb—O(8)
2,500(5) Pb—O(6) 2,178(8)
ɦɨɥɟɤɭɥɵ Cu(hfa)2 ɫ ɤɨɪɨɬɤɨɣ ɦɨɫɬɢɤɨɜɨɣ ɫɜɹɡɶɸ
Pb—O(6)
2,489(5) Pb—O(7) 2,577(8)
ɦɟɞɶ—ɤɢɫɥɨɪɨɞ ɫɨɨɬɜɟɬɫɬɜɭɸɬ ɭɞɥɢɧɟɧɧɵɟ ɯɟPb—O(7)
2,379(6) Pb—O(8) 2,511(9)
ɥɚɬɧɵɟ ɫɜɹɡɢ ɦɟɞɶ—ɤɢɫɥɨɪɨɞ ɢ ɦɨɫɬɢɤɨɜɵɟ ɫɜɹPb—O(1)
2,84
Pb—O(1)
3,11
ɡɢ ɫɜɢɧɟɰ—ɤɢɫɥɨɪɨɞ, ɚ ɞɥɹ ɞɪɭɝɨɣ ɦɨɥɟɤɭɥɵ
Pb—O(2)
2,94
Pb—O(2)
3,01
ɦɟɞɧɨɝɨ ɯɟɥɚɬɚ ɧɚɛɥɸɞɚɟɬɫɹ ɨɛɪɚɬɧɚɹ ɫɢɬɭɚɰɢɹ
Pb—O(3)
2,83
Pb—O(3)
2,97
(ɫɦ. ɬɚɛɥ. 2). Ɍɚɤɨɟ ɪɚɡɥɢɱɧɨɟ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɟ
Pb—O(4)
2,96
Pb—O(4)
3,31
ɩɨɜɟɞɟɧɢɟ ɚɬɨɦɚ ɦɟɞɢ ɫɤɚɡɵɜɚɟɬɫɹ ɧɚ ɫɬɪɭɤɬɭɪɟ
Cu(1)—O(1) 1,925(6) Cu(1)—O(1) 1,861(8)
ɦɨɥɟɤɭɥɵ ɫɜɢɧɰɨɜɨɝɨ ɤɨɦɩɥɟɤɫɚ, ɱɬɨ ɨɬɦɟɱɚɥɨɫɶ
Cu(1)—O(2) 1,929(6) Cu(1)—O(2) 1,881(8)
ɜɵɲɟ. ɋɥɟɞɭɟɬ ɬɚɤɠɟ ɨɬɦɟɬɢɬɶ ɭɜɟɥɢɱɟɧɢɟ ɭɝɥɚ
2,75 Cu(1)}O(7) 2,91
Cu(1)}O(8)
OPbO ɜ ɬɨɦ ɯɟɥɚɬɟ, ɝɞɟ ɚɬɨɦ ɤɢɫɥɨɪɨɞɚ ɬɟɫɧɟɟ
ɫɜɹɡɚɧ ɫ ɚɬɨɦɨɦ ɦɟɞɢ. ȼ ɞɪɭɝɨɦ ɯɟɥɚɬɟ ɷɬɨɝɨ ɠɟ
Cu(2)—O(3) 1,929(6) Cu(2)—O(3) 1,966(8)
ɫɜɢɧɰɨɜɨɝɨ ɤɨɦɩɥɟɤɫɚ, ɞɥɹ ɤɨɬɨɪɨɝɨ ɦɨɫɬɢɤɨɜɚɹ
Cu(2)—O(4) 1,910(6) Cu(2)—O(4) 1,996(9)
ɫɜɹɡɶ ɦɟɞɶ—ɤɢɫɥɨɪɨɞ ɛɨɥɟɟ ɞɥɢɧɧɚɹ, ɬɚɤɨɣ ɭɝɨɥ,
2,80 Cu(2)}O(5) 2,63
Cu(2)}O(6)
ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ, ɦɟɧɶɲɟ (ɫɦ. ɬɚɛɥ. 2). Ɍɚɤɢɦ ɨɛɪɚɍɝɨɥ
ɍɝɨɥ
Z
Z
ɡɨɦ, ɫɬɪɭɤɬɭɪɚ ɰɟɩɨɱɟɤ ɤɨɦɩɥɟɤɫɨɜ ɨɛɪɚɡɨɜɚɧO(5)PbO(7) 77,5(2) O(6)PbO(8) 78,7(3)
ɧɵɯ ɥɢɝɚɧɞɨɦ ɨɞɧɨɝɨ ɬɢɩɚ ɛɨɥɟɟ ɪɚɡɭɩɨɪɹɞɨɱɟO(6)PbO(8) 139,3(2) O(5)PbO(7) 139,4(3)
ɧɚ, ɱɟɦ ɜ Cu(ɚɚ)2˜Pb(hfa)2. Ɍɟɦ ɧɟ ɦɟɧɟɟ ɪɚɫɫɬɨɹO(5)PbO(8) 73,4(2) O(5)PbO(6) 79,5(3)
ɧɢɹ Pb…Cu ɜ ɰɟɩɨɱɤɟ Cu(hfa)2˜Pb(hfa)2 ɨɞɢɧɚɤɨO(6)PbO(7) 73,4(2) O(6)PbO(7) 70,9(3)
ɜɵ — 3,78 Å, ɱɬɨ ɧɟɫɤɨɥɶɤɨ ɛɨɥɶɲɟ, ɱɟɦ ɜ ɩɪɟɞɵɞɭɳɟɣ ɫɬɪɭɤɬɭɪɟ, ɧɨ ɦɟɧɶɲɟ, ɱɟɦ ɪɚɫɫɬɨɹɧɢɹ Pb…Pb ɜ ɢɧɞɢɜɢɞɭɚɥɶɧɨɦ Pb(hfa)2 [ 4 ].
ȼ ɤɪɢɫɬɚɥɥɚɯ ɢɡɭɱɟɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɤɚɠɞɚɹ ɰɟɩɨɱɤɚ ɦɨɥɟɤɭɥ CuL2˜PbL2 ɨɤɪɭɠɟɧɚ ɱɟɬɵɪɶɦɹ ɩɨɞɨɛɧɵɦɢ, ɫɜɹɡɚɧɧɵɦɢ ɥɢɛɨ ɬɪɚɧɫɥɹɰɢɹɦɢ, ɥɢɛɨ ɬɪɚɧɫɥɹɰɢɹɦɢ ɢ ɜɢɧɬɨɜɵɦɢ ɨɫɹɦɢ.
ɋɨɨɬɜɟɬɫɬɜɟɧɧɨ, ɜɞɨɥɶ ɨɫɢ X ɢ Z ɨɛɪɚɡɭɸɬɫɹ ɫɥɨɢ ɢɡ ɤɨɦɩɥɟɤɫɨɜ, ɧɚ ɜɧɟɲɧɢɯ ɩɨɜɟɪɯɧɨɫɬɹɯ
ɤɨɬɨɪɵɯ ɧɚɯɨɞɹɬɫɹ ɤɨɧɰɟɜɵɟ ɡɚɦɟɫɬɢɬɟɥɢ —CF3 (ɪɢɫ. 3).
ɂɡɜɟɫɬɧɨ, ɱɬɨ ɢɧɞɢɜɢɞɭɚɥɶɧɵɟ E-ɞɢɤɟɬɨɧɚɬɵ ɦɟɞɢ(II) ɢ ɫɜɢɧɰɚ(II) ɨɛɥɚɞɚɸɬ ɡɚɦɟɬɧɨɣ ɥɟɬɭɱɟɫɬɶɸ ɩɪɢ ɧɚɝɪɟɜɚɧɢɢ, ɩɨɷɬɨɦɭ ɧɚɦ ɛɵɥɨ ɢɧɬɟɪɟɫɧɨ ɩɪɨɜɟɪɢɬɶ ɬɟɪɦɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ ɩɨɥɭɱɟɧɵɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɵɯ ɫɨɟɞɢɧɟɧɢɣ. ɋɭɞɹ ɩɨ ɪɟɡɭɥɶɬɚɬɚɦ ɬɟɪɦɢɱɟɫɤɨɝɨ ɚɧɚɥɢɡɚ, ɩɨɥɭɱɟɧɧɵɟ ɫɨɟɞɢɧɟɧɢɹ ɜɟɞɭɬ ɫɟɛɹ ɩɨ-ɪɚɡɧɨɦɭ ɩɪɢ ɧɚɝɪɟɜɚɧɢɢ ɜ ɢɧɟɪɬɧɨɣ ɚɬɦɨɫɮɟɪɟ (ɪɢɫ. 4). Ɉɤɚɡɚɥɨɫɶ, ɱɬɨ ɝɨɦɨɥɢɝɚɧɞɧɨɟ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɨɟ ɫɨɟɞɢɧɟɧɢɟ ɧɚ ɨɫɧɨɜɟ ɝɟɤɫɚɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚ
Cu(hfa)2˜Pb(hfa)2 ɧɚɦɧɨɝɨ ɛɨɥɟɟ ɥɟɬɭɱɟɟ, ɱɟɦ Cu(ɚɚ)2˜Pb(hfa)2, ɱɬɨ ɫɨɜɩɚɞɚɟɬ ɫ ɢɡɜɟɫɬɧɨɣ ɬɟɧɞɟɧɰɢɟɣ ɭɜɟɥɢɱɟɧɢɹ ɥɟɬɭɱɟɫɬɢ E-ɞɢɤɟɬɨɧɚɬɨɜ ɷɬɢɯ ɦɟɬɚɥɥɨɜ ɫ ɭɜɟɥɢɱɟɧɢɟɦ ɫɨɞɟɪɠɚɧɢɹ ɮɬɨɪɚ
Ɋɢɫ. 2. Ɏɪɚɝɦɟɧɬ ɫɬɪɭɤɬɭɪɵ Cu(hfa)2˜Pb(hfa)2
ɄɊɂɋɌȺɅɅɂɑȿɋɄɂȿ ɋɌɊɍɄɌɍɊɕ Cu(aa)2˜Pb(hfa)2 ɂ Cu(hfa)˜Pb(hfa)2
1127
Ɋɢɫ. 3. ɉɪɨɟɤɰɢɹ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɢ ɧɚ ɩɥɨɫɤɨɫɬɶ XY ɞɥɹ
Cu(ɚɚ)2˜Pb(hfa)2 (ɚ), ɧɚ ɩɥɨɫɤɨɫɬɶ XZ ɞɥɹ Cu(hfɚ)2˜Pb(hfa)2 (ɛ)
Ɋɢɫ. 4. Ɋɟɡɭɥɶɬɚɬɵ ɬɟɪɦɨɝɪɚɜɢɦɟɬɪɢɱɟɫɤɨɝɨ ɚɧɚɥɢɡɚ
ɜ ɥɢɝɚɧɞɟ. ɋ ɞɪɭɝɨɣ ɫɬɨɪɨɧɵ, ɟɫɥɢ ɩɪɟɞɩɨɥɨɠɢɬɶ, ɱɬɨ
Cu(ɚɚ)2˜Pb(hfa)2 ɪɚɡɥɚɝɚɟɬɫɹ ɩɪɢ ɧɚɝɪɟɜɚɧɢɢ ɞɨ ɨɤɫɢɞɚ ɦɟɞɢ
ɢ ɨɤɫɢɞɚ ɫɜɢɧɰɚ, ɬɨ, ɫɭɞɹ ɩɨ ɤɨɥɢɱɟɫɬɜɭ ɨɫɬɚɬɤɚ, ɤɪɢɜɚɹ ɌȽ
ɞɥɹ ɞɚɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɨɬɜɟɱɚɟɬ ɜ ɨɫɧɨɜɧɨɦ ɩɪɨɰɟɫɫɭ ɪɚɡɥɨɠɟɧɢɹ.
ȼɕȼɈȾɕ
Ɉɛɳɢɦ
ɦɨɬɢɜɨɦ
ɞɥɹ
ɫɬɪɭɤɬɭɪ
ɫɨɟɞɢɧɟɧɢɣ
Cu(ɚɚ)2˜Pb(hfa)2 ɢ Cu(hfa)2˜Pb(hfa)2 ɹɜɥɹɟɬɫɹ ɬɨ, ɱɬɨ ɩɥɨɫɤɢɟ
ɦɨɥɟɤɭɥɵ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɞɢ(II) ɜɫɬɪɚɢɜɚɸɬɫɹ ɜ ɰɟɩɨɱɤɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɩɨɥɢɦɟɪɨɜ Eɞɢɤɟɬɨɧɚɬɨɜ ɫɜɢɧɰɚ(II) ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɱɬɨ ɩɪɨɢɫɯɨɞɢɬ ɱɟɪɟɞɨɜɚɧɢɟ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɨɜ ɦɟɬɚɥɥɨɜ. ɉɪɢ ɷɬɨɦ ɚɬɨɦɵ ɤɢɫɥɨɪɨɞɚ ɥɢɝɚɧɞɨɜ ɜɵɩɨɥɧɹɸɬ ɦɨɫɬɢɤɨɜɭɸ ɮɭɧɤɰɢɸ, ɢ Ʉɑ ɞɥɹ ɦɟɞɢ
ɫɬɚɧɨɜɢɬɫɹ ɪɚɜɧɵɦ 6, ɜ ɬɨ ɜɪɟɦɹ ɤɚɤ ɞɥɹ ɱɢɫɬɵɯ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɞɢ ɧɚɢɛɨɥɟɟ ɯɚɪɚɤɬɟɪɧɨ Ʉɑ 4.
Ɇɨɥɟɤɭɥɵ ɯɟɥɚɬɨɜ ɫɜɢɧɰɚ ɭɠɟ ɧɟ ɤɨɧɬɚɤɬɢɪɭɸɬ ɞɪɭɝ ɫ ɞɪɭɝɨɦ, ɯɨɬɹ ɢɯ ɜɡɚɢɦɧɚɹ ɨɪɢɟɧɬɚɰɢɹ
ɨɫɬɚɟɬɫɹ ɩɪɟɠɧɟɣ. ɉɨ ɷɬɨɣ ɩɪɢɱɢɧɟ ɚɬɨɦɵ ɮɬɨɪɚ ɭɠɟ ɧɟ ɭɱɚɫɬɜɭɸɬ ɜ ɤɨɨɪɞɢɧɚɰɢɢ, ɢ Ʉɑ 8 ɞɥɹ
ɫɜɢɧɰɚ ɪɟɚɥɢɡɭɟɬɫɹ ɩɭɬɟɦ ɞɨɩɨɥɧɢɬɟɥɶɧɵɯ ɤɨɧɬɚɤɬɨɜ ɰɟɧɬɪɚɥɶɧɨɝɨ ɚɬɨɦɚ ɫ ɚɬɨɦɚɦɢ ɤɢɫɥɨɪɨɞɚ
ɭɠɟ ɦɟɞɧɵɯ ɤɨɦɩɥɟɤɫɨɜ. Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɰɟɩɨɱɤɚ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɨɜ ɨɫɬɚɟɬɫɹ ɨɫɧɨɜɧɵɦ
ɫɬɪɭɤɬɭɪɨɨɛɪɚɡɭɸɳɢɦ ɷɥɟɦɟɧɬɨɦ ɢ ɜ ɩɨɥɭɱɟɧɧɵɯ ɝɟɬɟɪɨɤɨɦɩɥɟɤɫɧɵɯ ɫɨɟɞɢɧɟɧɢɹɯ. Ʉɨɨɪɞɢɧɚɰɢɨɧɧɨɟ ɩɨɜɟɞɟɧɢɟ ɚɬɨɦɚ ɦɟɞɢ ɫɭɳɟɫɬɜɟɧɧɨ ɦɟɧɹɟɬɫɹ ɜ ɡɚɜɢɫɢɦɨɫɬɢ ɨɬ ɬɢɩɚ ɥɢɝɚɧɞɚ, ɱɬɨ ɨɬɪɚɠɚɟɬɫɹ ɢ ɧɚ ɬɟɪɦɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜɚɯ ɢɡɭɱɟɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ.
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ. ɢ ɞɪ. // ɀɭɪɧ. ɫɬɪɭɤɬɭɪ. ɯɢɦɢɢ. – 1994. – 35, ʋ 3. – ɋ. 136 – 140.
Ʉɪɢɫɸɤ ȼ.ȼ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɨɥɶɲɚɤɨɜɚ ȿ.ȼ. // Ɍɚɦ ɠɟ. – ʋ 6. – ɋ. 197 – 201.
Krisyuk V.V., Baidina I.A., Gromilov S.A. et al. // J. Struct. Chem. – 1997. – 38, N 3. – P. 434 – 439.
Krisyuk V.V., Baidina I.A., Igumenov I.K. // Main Group Metal Chem. – 1998. – 21, N 4. – P. 199 – 206.
Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ. // ɀɭɪɧ. ɫɬɪɭɤɬɭɪ. ɯɢɦɢɢ. – 2004. – 4–5, ʋ 6. – ɋ. 1076 – 1127.
Sheldrick C.H. SHELX-76- Program for crystal determination – University of ɋambridge, England, 1976.
ɂɝɭɦɟɧɨɜ ɂ.Ʉ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ʉɪɚɞɟɧɨɜ Ʉ.ȼ. // ɂɡɜ. ɋɈ Ⱥɇ ɋɋɋɊ. Cɟɪ. ɯɢɦ. – 1989. – ȼɵɩ. 5. –
ɋ. 21 – 30.
8. ɋɬɚɪɢɤɨɜɚ Ɂ.Ⱥ., ɒɭɝɚɦ ȿ.Ⱥ. // ɀɭɪɧ. ɫɬɪɭɤɬɭɪ. ɯɢɦɢɢ. – 1969.– 10, ʋ 2. – ɋ. 290 – 293.
9. Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ. ɢ ɞɪ. // Ɍɚɦ ɠɟ. – 2004. – 45, ʋ 3. – ɋ. 502 – 507.
1.
2.
3.
4.
5.
6.
7.