ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɍɨɦ 48, ʋ 3 Ɇɚɣ – ɢɸɧɶ ɋ. 537 – 542

ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2007. Ɍɨɦ 48, ʋ 3
Ɇɚɣ – ɢɸɧɶ
ɋ. 537 – 542
ɍȾɄ 546.723+547.442
ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɂ ɆɈɅȿɄɍɅəɊɇȺə ɋɌɊɍɄɌɍɊȺ
ɌɊɂɋ-(1,1,1-ɌɊɂɎɌɈɊ-5,5-ȾɂɆȿɌɂɅȽȿɄɋȺɇ-2,4-ȾɂɈɇȺɌɈ) ɀȿɅȿɁȺ(III)
” 2007 ɂ.Ⱥ. Ȼɚɣɞɢɧɚ*, ɇ.ȼ. Ʉɭɪɚɬɶɟɜɚ, ɉ.Ⱥ. ɋɬɚɛɧɢɤɨɜ, ɋ.Ⱥ. Ƚɪɨɦɢɥɨɜ
ɂɧɫɬɢɬɭɬ ɧɟɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɢɦ. Ⱥ.ȼ. ɇɢɤɨɥɚɟɜɚ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 1 ɢɸɧɹ 2006 ɝ.
ɉɪɢɜɟɞɟɧɵ ɫɢɧɬɟɡ ɢ ɪɟɡɭɥɶɬɚɬɵ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɢɫɫɥɟɞɨɜɚɧɢɹ ɬɪɢɫ(ɩɢɜɚɥɨɢɥɬɪɢɮɬɨɪɚɰɟɬɨɧɚɬɨ)ɠɟɥɟɡɚ(III). Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ C24H30FeF9O6:
a = 9,2205(6), b = 9,6584(10), c = 17,3799(17) Å, D = 75,902(2), E = 80,517(3), J =
= 82,746(3)q, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Ɋ-1, V = 1474,6(2) Å3, Z = 2. ɋɬɪɭɤɬɭɪɚ ɦɨɥɟɤɭɥɹɪɧɚɹ, ɨɤɪɭɠɟɧɢɟ ɚɬɨɦɚ Fe ɨɤɬɚɷɞɪɢɱɟɫɤɨɟ, Fe—Oɫɪ 1,991 Å, ‘Ɉ—Fe—Oɫɪ 86,48q. Ɋɚɫɫɱɢɬɚɧɚ ɷɧɟɪɝɢɹ ɦɟɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ. Ɋɚɫɫɱɢɬɚɧɧɵɟ
ɜɟɥɢɱɢɧɵ ɫɨɩɨɫɬɚɜɥɟɧɵ ɫ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɦɢ ɞɚɧɧɵɦɢ.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : E-ɞɢɤɟɬɨɧɚɬɵ ɠɟɥɟɡɚ(III), ɤɪɢɫɬɚɥɥɢɱɟɫɤɚɹ ɢ ɦɨɥɟɤɭɥɹɪɧɚɹ
ɫɬɪɭɤɬɭɪɚ.
ȼȼȿȾȿɇɂȿ
E-Ⱦɢɤɟɬɨɧɚɬɵ ɠɟɥɟɡɚ(III) ɯɨɬɹ ɢ ɧɟ ɧɚɯɨɞɹɬ ɫɬɨɥɶ ɲɢɪɨɤɨɝɨ ɩɪɢɦɟɧɟɧɢɹ, ɤɚɤ ɤɨɦɩɥɟɤɫɵ
ɧɟɤɨɬɨɪɵɯ ɞɪɭɝɢɯ ɦɟɬɚɥɥɨɜ, ɹɜɥɹɸɬɫɹ ɧɚɢɛɨɥɟɟ ɢɡɭɱɟɧɧɵɦɢ ɫɪɟɞɢ ɜɫɟɯ ɬɪɢɫ-E-ɞɢɤɟɬɨɧɚɬɨɜ
ɬɪɟɯɜɚɥɟɧɬɧɵɯ ɦɟɬɚɥɥɨɜ. ɗɬɨ ɨɛɴɹɫɧɹɟɬɫɹ ɞɨɫɬɭɩɧɨɫɬɶɸ ɪɟɚɝɟɧɬɨɜ ɢ ɭɞɨɛɫɬɜɨɦ ɪɚɛɨɬɵ ɫ ɷɬɢɦ
ɦɟɬɚɥɥɨɦ: ɩɨɱɬɢ ɤɨɥɢɱɟɫɬɜɟɧɧɵɟ ɜɵɯɨɞɵ ɩɪɢ ɫɢɧɬɟɡɟ, ɩɪɨɫɬɨɬɚ ɨɱɢɫɬɤɢ, ɭɫɬɨɣɱɢɜɨɫɬɶ ɩɪɢ
ɯɪɚɧɟɧɢɢ ɜ ɨɛɵɱɧɵɯ ɭɫɥɨɜɢɹɯ. Ʉ ɧɚɫɬɨɹɳɟɦɭ ɜɪɟɦɟɧɢ ɜ ɯɢɦɢɱɟɫɤɨɦ [ 1, 2 ] ɢ ɜ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɨɦ [ 3, 4 ] ɩɥɚɧɚɯ E-ɞɢɤɟɬɨɧɚɬɵ ɠɟɥɟɡɚ(III) ɞɨɫɬɚɬɨɱɧɨ ɯɨɪɨɲɨ ɢɫɫɥɟɞɨɜɚɧɵ. ɂɡɜɟɫɬɧɵ ɢ
ɫɬɪɭɤɬɭɪɧɵɟ ɪɚɫɲɢɮɪɨɜɤɢ ɷɬɢɯ ɤɨɦɩɥɟɤɫɨɜ, ɤɨɬɨɪɵɟ ɩɪɢɜɟɞɟɧɵ ɜ Ʉɟɦɛɪɢɞɠɫɤɨɦ ɛɚɧɤɟ ɫɬɪɭɤɬɭɪɧɵɯ ɞɚɧɧɵɯ [ 5—10 ]. Ⱦɚɧɧɵɟ ɨ ɮɢɡɢɱɟɫɤɢɯ ɫɜɨɣɫɬɜɚɯ ɢ ɧɟɤɨɬɨɪɵɟ ɝɟɨɦɟɬɪɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɦɨɥɟɤɭɥ ɲɟɫɬɢ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III) ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 1.
ɇɚɫɬɨɹɳɚɹ ɪɚɛɨɬɚ ɩɪɨɞɨɥɠɚɟɬ ɤɪɢɫɬɚɥɥɨɯɢɦɢɱɟɫɤɨɟ ɢɫɫɥɟɞɨɜɚɧɢɟ ɤɨɦɩɥɟɤɫɨɜ ɞɚɧɧɨɝɨ
ɦɟɬɚɥɥɚ ɢ ɩɨɫɜɹɳɟɧɚ ɨɩɪɟɞɟɥɟɧɢɸ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɵ ɥɟɬɭɱɟɝɨ ɤɨɦɩɥɟɤɫɚ ɠɟɥɟɡɚ ɫ
ɧɟɫɢɦɦɟɬɪɢɱɧɵɦ ɥɢɝɚɧɞɨɦ 1,1,1-ɬɪɢɮɬɨɪ-5,5-ɞɢɦɟɬɢɥ-2,4-ɝɟɤɫɚɧɞɢɨɧɨɦ — ɩɢɜɚɥɨɢɥɬɪɢɮɬɨɪɚɰɟɬɨɧɨɦ (Hptf), ɤɨɬɨɪɵɣ ɫɨɞɟɪɠɢɬ ɡɚɦɟɫɬɢɬɟɥɢ ɮɬɨɪɢɪɨɜɚɧɧɵɣ CF3 ɢ ɨɛɴɟɦɧɵɣ C(CH3)3.
ɉɪɟɞɜɚɪɢɬɟɥɶɧɵɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɞɥɹ ɷɬɨɝɨ ɤɨɦɩɥɟɤɫɚ ɩɪɢɜɟɞɟɧɵ ɪɚɛɨɬɟ [ 11 ].
ɗɄɋɉȿɊɂɆȿɇɌȺɅɖɇȺə ɑȺɋɌɖ
ɂɫɩɨɥɶɡɨɜɚɥɢ ɷɬɚɧɨɥ, CHCl3 ɤɜɚɥɢɮɢɤɚɰɢɢ sɱ.s, FeCl3˜6H2O, NaOH ɤɜɚɥɢɮɢɤɚɰɢɢ sɱ.ɞ.ɚ.s,
Hptf 99%-ɨɣ ɱɢɫɬɨɬɵ ɢ ɫɢɥɢɤɚɝɟɥɶ L100/160P.
ɋɢɧɬɟɡ ɬɪɢɫ(ɩɢɜɚɥɨɢɥɬɪɢɮɬɨɪɚɰɟɬɨɧɚɬɨ)ɠɟɥɟɡɚ(III) (Fe(ɪtf)3) ɩɪɨɜɨɞɢɥɢ ɜ ɜɨɞɧɨɷɬɚɧɨɥɶɧɨɣ ɫɪɟɞɟ ɩɨ ɦɟɬɨɞɢɤɟ, ɨɩɢɫɚɧɧɨɣ ɜ ɪɚɛɨɬɚɯ [ 1, 4 ]. Ʉ ɪɚɫɬɜɨɪɭ ɯɥɨɪɢɞɚ ɠɟɥɟɡɚ(III) ɩɪɢɥɢɜɚɥɢ ɪɚɫɬɜɨɪ Hptf, ɧɟɣɬɪɚɥɢɡɨɜɚɧɧɨɝɨ NaOH. Ɉɛɪɚɡɨɜɚɜɲɟɟɫɹ ɤɪɚɫɧɨɟ ɦɚɫɥɨ ɩɪɨɦɵɜɚɥɢ ɜɨɞɨɣ ɢ ɫɭɲɢɥɢ ɧɚ ɜɨɡɞɭɯɟ. Ⱦɥɹ ɨɱɢɫɬɤɢ ɷɬɨɝɨ ɤɨɦɩɥɟɤɫɚ ɬɚɤɢɟ ɦɟɬɨɞɵ, ɤɚɤ ɩɟɪɟɤɪɢɫɬɚɥɥɢɡɚɰɢɹ
ɢ ɫɭɛɥɢɦɚɰɢɹ, ɧɟɷɮɮɟɤɬɢɜɧɵ. Ɉɤɨɧɱɚɬɟɥɶɧɭɸ ɨɱɢɫɬɤɭ ɤɨɦɩɥɟɤɫɚ ɩɪɨɜɨɞɢɥɢ ɯɪɨɦɚɬɨɝɪɚɮɢɱɟɫɤɢ
* E-mail: [email protected]
538
ɂ.Ⱥ. ȻȺɃȾɂɇȺ, ɇ.ȼ. ɄɍɊȺɌɖȿȼȺ, ɉ.Ⱥ. ɋɌȺȻɇɂɄɈȼ, ɋ.Ⱥ. ȽɊɈɆɂɅɈȼ
Ɍɚɛɥɢɰɚ 1
Ɏɢɡɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɢ ɧɟɤɨɬɨɪɵɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɞɥɹ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III)
ɉɚɪɚɦɟɬɪ
Fe(aa)3
[5]
Fe(hfa)3
[6]
Fe(dpm)3
[7]
Fe(dbm)3
D[8]
E[9]
Fe(tfa)3
[ 10 ]
Fe(ptf)3
ɇɚɫɬ. ɪɚɛɨɬɚ
Mɨɥɟɤɭɥɹɪ353,2
677,0
605,7
725,6
515,1
641,3
ɧɵɣ ɜɟɫ
T, K
453
328
437
534
530
388
326
Ecalc,
121,1
95,7
142,7
250,6
107,7
127,2
ɤȾɠ/ɦɨɥɶ
ǻHsubl,
125,4r0,6
104,1r1,3
120,6r0,8
141,6r3,9
ɤȾɠ/ɦɨɥɶ
ǻSsubl,
226,9r1,5
257,4r4,1
221,3r2,0
175,0r7,9
Ⱦɠ/ɦɨɥɶ /K
T1—T2, K
353–458
303–326
388–436
455–530
T1/2, K
480
365
490
640
640
445
440
1,56
0,91
2,02
2,66
4,27
5,05
P, D [18]
k, %
65,1
63,4
58,5
66,7
63,6
63,3
586,2
947,1
513,7
737,3
Vmol, Å3
dcalc, ɝ/ɫɦ3
1,92
1,061
1,67
1,44
Fe—O, Å 1,986–2,004 1,986–2,002 1,983–2,022 1,963–2,008 1,970–2,018 1,944–2,036 1,968–2,013
O—Fe—O, 86,7–87,3
86,4–87,6
85,2
85,5–87,2
85,7–87,1
86,4–88,2 86,22–86,64
ɝɪɚɞ.
Fe…Fe, Å 7,557–8,299 7,886–10,444 8,677–12,409 8,776–10,686 9,073–10,078 7,37–10,2 8,477–10,594
n
8
4
8
2
2
8
8
ɉ ɪ ɢ ɦ ɟ ɱ ɚ ɧ ɢ ɹ. Fe(aa)3 — ɚɰɟɬɢɥɚɰɟɬɨɧɚɬ Fe(III), Fe(tfa)3 — ɬɪɢɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬ Fe(III),
Fe(hfa)3 — ɝɟɤɫɚɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬ Fe(III), Fe(ptf)3 — ɩɢɜɚɥɨɢɥɬɪɢɮɬɨɪɚɰɟɬɨɧɚɬ Fe(III), Fe(dpm)3 —
ɞɢɩɢɜɚɥɨɢɥɦɟɬɚɧɚɬ Fe(III), Fe(dbm)3 — ɞɢɛɟɧɡɨɢɥɦɟɬɚɧɚɬ Fe(III).
Ecalc — ɪɚɫɱɟɬɧɚɹ ɷɧɟɪɝɢɹ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ; ǻHsubl — ɷɧɬɚɥɶɩɢɹ ɫɭɛɥɢɦɚɰɢɢ;
ǻSsubl — ɷɧɬɪɨɩɢɹ ɫɭɛɥɢɦɚɰɢɢ; T1—T2 — ɬɟɦɩɟɪɚɬɭɪɧɵɣ ɢɧɬɟɪɜɚɥ ɢɡɦɟɪɟɧɢɹ ǻHsubl ɢ ǻSsubl; T1/2 —
ɬɟɦɩɟɪɚɬɭɪɚ ɩɨɥɭɢɫɩɚɪɟɧɢɹ ɧɚɜɟɫɤɢ (ɞɚɧɧɵɟ ȾɌȺ); P — ɞɢɩɨɥɶɧɵɣ ɦɨɦɟɧɬ ɦɨɥɟɤɭɥ ɜ ɪɚɫɬɜɨɪɟ; k —
ɩɥɨɬɧɨɫɬɶ ɭɩɚɤɨɜɤɢ, ɪɚɫɫɱɢɬɚɧɧɚɹ ɩɨ ɩɪɨɝɪɚɦɦɟ PLATON (www.cryst.chem.uu.nl/platon); n — ɱɢɫɥɨ
ɛɥɢɠɚɣɲɢɯ ɦɨɥɟɤɭɥ ɜ ɤɪɢɫɬɚɥɥɟ.
ɧɚ ɫɢɥɢɤɚɝɟɥɟ, ɷɥɸɢɪɭɸɳɢɦ ɪɚɫɬɜɨɪɢɬɟɥɟɦ ɫɥɭɠɢɥ CHCl3 (ɜɵɯɨɞ a 80 %). Ɉɱɢɳɟɧɧɵɣ Fe(ɪtf)3
ɩɪɟɞɫɬɚɜɥɹɟɬ ɫɨɛɨɣ ɤɪɚɫɧɵɣ ɩɨɪɨɲɨɤ ɫ Ɍɩɥ = 53—54 qɋ (ɫɬɨɥɢɤ Ȼɨɷɰɢɭɫɚ). ɋɨɟɞɢɧɟɧɢɟ ɯɨɪɨɲɨ
ɪɚɫɬɜɨɪɢɦɨ ɜ ɛɨɥɶɲɢɧɫɬɜɟ ɨɪɝɚɧɢɱɟɫɤɢɯ ɪɚɫɬɜɨɪɢɬɟɥɟɣ. Ɋɟɡɭɥɶɬɚɬɵ ɯɢɦɢɱɟɫɤɨɝɨ ɚɧɚɥɢɡɚ ɜ %
(ɧɚɣɞɟɧɨ/ɪɚɫɫɱɢɬɚɧɨ) ɞɥɹ C24H30FeF9O6: C 45,2/45,0; H 5,1/4,7; F 26,1/26,7.
Fe(ɪtf)3 ɨɛɥɚɞɚɟɬ ɥɟɬɭɱɟɫɬɶɸ ɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ ɜɵɲɟ 120 qɋ ɥɟɝɤɨ ɩɟɪɟɯɨɞɢɬ ɜ ɝɚɡɨɜɭɸ
ɮɚɡɭ. ɇɚ ɪɢɫ. 1 ɩɪɢɜɟɞɟɧɵ ɬɟɪɦɨɝɪɚɜɢɦɟɬɪɢɱɟɫɤɢɟ ɤɪɢɜɵɟ ɩɨɬɟɪɢ ɦɚɫɫɵ ɧɟɤɨɬɨɪɵɯ Eɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III), ɩɨɥɭɱɟɧɧɵɟ ɧɚ ɞɟɪɢɜɚɬɨɝɪɚɮɟ Q1500-D (ɮɢɪɦɚ ɆɈɆ, ȼɟɧɝɪɢɹ) ɜ ɨɬɤɪɵɬɨɦ ɬɢɝɥɟ ɩɪɢ
ɫɤɨɪɨɫɬɢ ɧɚɝɪɟɜɚ 5 ɝɪɚɞ./ɦɢɧ. Ʉɚɤ ɫɥɟɞɭɟɬ ɢɡ ɪɢɫ. 1, ɞɚɧɧɵɣ ɤɨɦɩɥɟɤɫ ɩɨ ɥɟɬɭɱɟɫɬɢ ɭɫɬɭɩɚɟɬ ɬɨɥɶɤɨ ɝɟɤɫɚɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬɭ ɠɟɥɟɡɚ(III) ɢ ɛɥɢɡɨɤ ɩɨ ɥɟɬɭɱɟɫɬɢ ɤ
ɬɪɢɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬɭ ɠɟɥɟɡɚ(III).
Ɋɟɧɬɝɟɧɨɝɪɚɮɢɱɟɫɤɨɟ ɢɫɫɥɟɞɨɜɚɧɢɟ ɩɨɥɢɤɪɢɫɬɚɥɥɨɜ
Ɋɢɫ. 1. Ʉɪɢɜɵɟ ɩɨɬɟɪɢ ɦɚɫɫɵ ɞɥɹ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III):
1 — Fe(hfa)3, 2 — Fe(ptf)3, 3 — Fe(tfa)3, 4 — Fe(aa)3,
5 — Fe(dpm)3, 6 — Fe(dbm)3
539
ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɂ ɆɈɅȿɄɍɅəɊɇȺə ɋɌɊɍɄɌɍɊȺ C24H30FeF9O6
Ɍɚɛɥɢɰɚ 2
Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ Fe(ptf)3
Ɏɨɪɦɭɥɚ
Ɇɨɥɟɤɭɥɹɪɧɚɹ ɦɚɫɫɚ
Ɍɟɦɩɟɪɚɬɭɪɚ, K
Ⱦɥɢɧɚ ɜɨɥɧɵ, Å
ɉɪ. ɝɪɭɩɩɚ
ɉɚɪɚɦɟɬɪɵ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɢ:
a, b, c, Å
DEJɝɪɚɞ.
V, Å3
Z
ɉɥɨɬɧɨɫɬɶ (ɪɚɫɫɱɢɬɚɧɧɚɹ), ɝ/ɫɦ3
Ʉɨɷɮɮɢɰɢɟɧɬ ɩɨɝɥɨɳɟɧɢɹ, ɦɦ–1
F(000)
Ⱦɢɚɩɚɡɨɧ T, ɝɪɚɞ.
Ʉɨɥɢɱɟɫɬɜɨ ɪɟɮɥɟɤɫɨɜ
ɑɢɫɥɨ ɧɟɡɚɜɢɫɢɦɵɯ ɪɟɮɥɟɤɫɨɜ
ɉɨɥɧɨɬɚ ɫɛɨɪɚ ɞɚɧɧɵɯ (T = 25,00q), %
Ɇɟɬɨɞ ɭɬɨɱɧɟɧɢɹ
Ʉɨɥɢɱɟɫɬɜɨ ɪɟɮɥɟɤɫɨɜ / ɨɝɪɚɧɢɱɟɧɢɣ / ɩɚɪɚɦɟɬɪɨɜ
GOOF ɞɥɹ F 2
R-ɮɚɤɬɨɪ [I ! 2V(I )]
R-ɮɚɤɬɨɪ (ɜɫɟ ɞɚɧɧɵɟ)
Ɉɫɬɚɬɨɱɧɚɹ ɷɥɟɤɬɪɨɧɧɚɹ ɩɥɨɬɧɨɫɬɶ (min/max), e, Å–3
C24H30F9FeO6
641,33
243(2)
0,71073
P-1
9,2205(6), 9,6584(10), 17,3799(17)
75,902(2), 80,517(3), 82,746(3)
1474,6(2)
2
1,444
0,603
658
2,40—26,37
10972
5763 [R(int) = 0,0420]
96,2
ɉɨɥɧɨɦɚɬɪɢɱɧɵɣ ɆɇɄ ɩɨ F 2
5763 / 0 / 455
0,885
R1 = 0,0470, wR2 = 0,0977
R1 = 0,1141, wR2 = 0,1123
0,244 / –0,201
Ɍɚɛɥɢɰɚ 3
Ɉɫɧɨɜɧɵɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ d (Å) ɢ ɭɝɥɵ Z (ɝɪɚɞ.) ɞɥɹ Fe(ptf)3
ɋɜɹɡɶ
d
ɋɜɹɡɶ
d
ɍɝɨɥ
Z
Fe(1)—O(21)
Fe(1)—O(11)
Fe(1)—O(31)
Fe(1)—O(22)
Fe(1)—O(32)
Fe(1)—O(12)
O(11)—C(12)
O(12)—C(14)
O(21)—C(22)
O(22)—C(24)
O(31)—C(32)
O(32)—C(34)
C(11)—C(12)
C(12)—C(13)
C(13)—C(14)
C(14)—C(15)
C(21)—C(22)
C(22)—C(23)
C(23)—C(24)
C(24)—C(25)
C(31)—C(32)
1,968(2)
1,978(2)
1,981(2)
1,9950(19)
2,013(2)
2,013(2)
1,274(3)
1,257(3)
1,273(3)
1,267(3)
1,276(4)
1,253(3)
1,519(4)
1,359(4)
1,413(4)
1,528(4)
1,525(4)
1,357(4)
1,402(4)
1,523(4)
1,528(5)
C(32)—C(33)
C(33)—C(34)
C(34)—C(35)
C(15A)—C(15)
C(15B)—C(15)
C(15C)—C(15)
C(25A)—C(25)
C(25B)—C(25)
C(25C)—C(25)
C(35A)—C(35)
C(35B)—C(35)
C(35C)—C(35)
F(11A)—C(11)
F(11B)—C(11)
F(11C)—C(11)
F(21A)—C(21)
F(21B)—C(21)
F(21C)—C(21)
F(31A)—C(31)
F(31B)—C(31)
1,354(4)
1,409(4)
1,522(4)
1,534(4)
1,540(4)
1,529(4)
1,545(5)
1,535(5)
1,495(5)
1,527(5)
1,519(4)
1,511(5)
1,307(7)
1,292(8)
1,290(7)
1,280(8)
1,305(10)
1,298(8)
1,325(16)
1,315(13)
O(21)—Fe(1)—O(22)
O(31)—Fe(1)—O(32)
O(11)—Fe(1)—O(12)
C(12)—O(11)—Fe(1)
C(14)—O(12)—Fe(1)
C(22)—O(21)—Fe(1)
C(24)—O(22)—Fe(1)
C(32)—O(31)—Fe(1)
C(34)—O(32)—Fe(1)
O(11)—C(12)—C(13)
C(12)—C(13)—C(14)
O(12)—C(14)—C(13)
O(21)—C(22)—C(23)
C(22)—C(23)—C(24)
O(22)—C(24)—C(23)
O(31)—C(32)—C(33)
C(32)—C(33)—C(34)
O(32)—C(34)—C(33)
86,57(8)
86,22(8)
86,64(8)
125,91(19)
130,77(19)
125,1(2)
129,4(2)
124,6(2)
129,2(2)
128,6(3)
123,2(3)
121,8(3)
128,0(3)
123,7(3)
121,0(3)
128,7(3)
122,8(3)
122,1(3)
540
ɂ.Ⱥ. ȻȺɃȾɂɇȺ, ɇ.ȼ. ɄɍɊȺɌɖȿȼȺ, ɉ.Ⱥ. ɋɌȺȻɇɂɄɈȼ, ɋ.Ⱥ. ȽɊɈɆɂɅɈȼ
Fe(ɪtf)3 ɩɪɨɜɟɞɟɧɨ ɧɚ ɞɢɮɪɚɤɬɨɦɟɬɪɟ ȾɊɈɇ-3M (CuKD-ɢɡɥɭɱɟɧɢɟ, Ni-ɮɢɥɶɬɪ, ɨɛɥɚɫɬɶ ɭɝɥɨɜ 2T
ɨɬ 5 ɞɨ 40q, ɤɨɦɧɚɬɧɚɹ ɬɟɦɩɟɪɚɬɭɪɚ). Ʉɨɦɩɥɟɤɫ ɢɫɬɢɪɚɥɢ ɜɫɭɯɭɸ ɢ ɧɚɫɟɢɜɚɥɢ ɧɚ ɩɨɥɢɪɨɜɚɧɧɭɸ
ɫɬɨɪɨɧɭ ɫɬɚɧɞɚɪɬɧɨɣ ɤɜɚɪɰɟɜɨɣ ɤɸɜɟɬɵ, ɫɦɚɡɚɧɧɭɸ ɮɬɨɪɢɪɨɜɚɧɧɵɦ ɦɚɫɥɨɦ.
Ɇɨɧɨɤɪɢɫɬɚɥɥɵ ɞɥɹ ɊɋȺ ɜɵɪɚɳɟɧɵ ɦɟɞɥɟɧɧɵɦ ɢɫɩɚɪɟɧɢɟɦ ɝɟɩɬɚɧɨɜɨɝɨ ɪɚɫɬɜɨɪɚ ɤɨɦɩɥɟɤɫɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. ɋɨɟɞɢɧɟɧɢɟ ɤɪɢɫɬɚɥɥɢɡɭɟɬɫɹ ɜ ɜɢɞɟ ɩɪɢɡɦ ɤɢɪɩɢɱɧɨɤɪɚɫɧɨɝɨ ɰɜɟɬɚ. Ⱦɥɹ ɪɚɫɲɢɮɪɨɜɤɢ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɵ ɢɡɦɟɪɟɧɵ ɩɚɪɚɦɟɬɪɵ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɢ ɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ –30 qC ɧɚ ɚɜɬɨɦɚɬɢɱɟɫɤɨɦ ɱɟɬɵɪɟɯɤɪɭɠɧɨɦ ɞɢɮɪɚɤɬɨɦɟɬɪɟ Bruker-Nonius X8-Apex, ɨɫɧɚɳɟɧɧɨɦ ɞɜɭɯɤɨɨɪɞɢɧɚɬɧɵɦ ɞɟɬɟɤɬɨɪɨɦ (MoKD-ɢɡɥɭɱɟɧɢɟ, ɝɪɚɮɢɬɨɜɵɣ ɦɨɧɨɯɪɨɦɚɬɨɪ). Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ
ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɢ ɨɫɧɨɜɧɵɟ ɩɚɪɚɦɟɬɪɵ ɷɤɫɩɟɪɢɦɟɧɬɚ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 2. ɋɬɪɭɤɬɭɪɚ ɪɟɲɟɧɚ
ɩɪɹɦɵɦ ɦɟɬɨɞɨɦ ɢ ɭɬɨɱɧɟɧɚ ɜ ɚɧɢɡɨɬɪɨɩɧɨ-ɢɡɨɬɪɨɩɧɨɦ (ɞɥɹ ɇ) ɩɪɢɛɥɢɠɟɧɢɢ, ɚɬɨɦɵ ɜɨɞɨɪɨɞɚ
ɡɚɞɚɧɵ ɝɟɨɦɟɬɪɢɱɟɫɤɢ. ȼ ɤɨɧɰɟɜɵɯ ɡɚɦɟɫɬɢɬɟɥɹɯ ɚɬɨɦɵ ɮɬɨɪɚ CF3-ɝɪɭɩɩ ɪɚɡɭɩɨɪɹɞɨɱɟɧɵ ɩɨ
ɞɜɭɦ ɩɨɡɢɰɢɹɦ. Ɉɫɧɨɜɧɵɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ ɤɨɦɩɥɟɤɫɚ ɩɪɢɜɟɞɟɧɵ
ɜ ɬɚɛɥ. 3. ȼɫɟ ɪɚɫɱɟɬɵ ɜɵɩɨɥɧɟɧɵ ɩɨ ɤɨɦɩɥɟɤɫɭ ɩɪɨɝɪɚɦɦ SHELXTL [ 12 ]. Ⱦɢɮɪɚɤɬɨɝɪɚɦɦɚ
ɫɨɟɞɢɧɟɧɢɹ ɩɨɥɧɨɫɬɶɸ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɞɚɧɧɵɦ ɢɫɫɥɟɞɨɜɚɧɢɹ ɦɨɧɨɤɪɢɫɬɚɥɥɚ ɢ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ
ɨɛ ɨɞɧɨɮɚɡɧɨɫɬɢ ɢɫɫɥɟɞɭɟɦɨɝɨ ɩɪɨɞɭɤɬɚ.
ɊȿɁɍɅɖɌȺɌɕ ɂ ɂɏ ɈȻɋɍɀȾȿɇɂȿ
ɋɬɪɭɤɬɭɪɚ ɢɫɫɥɟɞɨɜɚɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ Fe(ptf)3 ɦɨɥɟɤɭɥɹɪɧɚɹ, ɩɨɫɬɪɨɟɧɚ ɢɡ ɨɬɞɟɥɶɧɵɯ ɦɨɥɟɤɭɥ ɝɪɚɧ-ɤɨɦɩɥɟɤɫɚ (faɫial-ɫomplex), ɫɬɪɨɟɧɢɟ ɤɨɬɨɪɨɝɨ ɫ ɧɭɦɟɪɚɰɢɟɣ ɚɬɨɦɨɜ ɩɨɤɚɡɚɧɨ ɧɚ
ɪɢɫ. 2. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɞɢɩɨɥɶɧɵɣ ɦɨɦɟɧɬ Fe(ptf)3, ɭɫɬɚɧɨɜɥɟɧɧɵɣ ɧɚɦɢ ɜ [ 13 ], ɪɚɜɟɧ
5,05 D. Ȼɨɥɶɲɨɣ ɞɢɩɨɥɶɧɵɣ ɦɨɦɟɧɬ (4,27 D [ 13 ] ) ɧɚɣɞɟɧ ɢ ɞɥɹ ɬɪɢɮɬɨɪɚɰɟɬɢɥɚɰɟɬɨɧɚɬɚ ɠɟɥɟɡɚ(III), ɤɪɢɫɬɚɥɥɵ ɤɨɬɨɪɨɝɨ ɩɨɫɬɪɨɟɧɵ ɬɚɤɠɟ ɢɡ ɝɪɚɧ-ɤɨɦɩɥɟɤɫɨɜ [ 10 ]. ɍ ɤɨɦɩɥɟɤɫɨɜ ɫ ɫɢɦɦɟɬɪɢɱɧɵɦɢ ɥɢɝɚɧɞɚɦɢ ɞɢɩɨɥɶɧɵɟ ɦɨɦɟɧɬɵ ɫɭɳɟɫɬɜɟɧɧɨ ɦɟɧɶɲɟ (ɫɦ. ɬɚɛɥ. 1).
Ⱥɬɨɦ ɠɟɥɟɡɚ ɢɦɟɟɬ ɨɛɵɱɧɨɟ ɞɥɹ E-ɞɢɤɟɬɨɧɚɬɧɵɯ ɤɨɦɩɥɟɤɫɨɜ ɠɟɥɟɡɚ(III) ɨɤɬɚɷɞɪɢɱɟɫɤɨɟ
ɨɤɪɭɠɟɧɢɟ ɢɡ ɲɟɫɬɢ ɚɬɨɦɨɜ ɤɢɫɥɨɪɨɞɚ, ɩɪɢɧɚɞɥɟɠɚɳɢɯ ɬɪɟɦ E-ɞɢɤɟɬɨɧɚɬɧɵɦ ɥɢɝɚɧɞɚɦ. Ɂɧɚɱɟɧɢɹ ɞɥɢɧ ɫɜɹɡɟɣ Fe—O ɥɟɠɚɬ ɜ ɢɧɬɟɪɜɚɥɟ 1,968—2,013 Å, ɪɚɫɫɬɨɹɧɢɟ Fe—Oɫɪ ɫɨ ɫɬɨɪɨɧɵ
ɮɬɨɪɢɪɨɜɚɧɧɨɝɨ ɡɚɦɟɫɬɢɬɟɥɹ ɧɚ 0,03 Å ɤɨɪɨɱɟ, ɱɟɦ ɫɨ ɫɬɨɪɨɧɵ But-ɡɚɦɟɫɬɢɬɟɥɹ. ɏɟɥɚɬɧɵɣ ɜɚɥɟɧɬɧɵɣ ɭɝɨɥ ‘Ɉ—Fe—Oɫɪ 86,48q. Ƚɟɨɦɟɬɪɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɨɝɨ ɭɡɥɚ
ɯɨɪɨɲɨ ɫɨɝɥɚɫɭɸɬɫɹ ɫ ɥɢɬɟɪɚɬɭɪɧɵɦɢ ɞɚɧɧɵɦɢ ɞɥɹ ɞɪɭɝɢɯ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III), ɩɪɢɜɟɞɟɧɧɵɦɢ ɜ ɬɚɛɥ. 1. Ƚɟɨɦɟɬɪɢɹ ɬɪɟɯ ɤɨɨɪɞɢɧɢɪɨɜɚɧɧɵɯ ɥɢɝɚɧɞɨɜ ɨɛɵɱɧɚ ɢ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɞɚɧɧɵɦ ɩɨ ɞɪɭɝɢɦ ɫɨɟɞɢɧɟɧɢɹɦ ɫ ɭɱɚɫɬɢɟɦ ptf-ɥɢɝɚɧɞɚ: Cu(ptf)2 [ 14, 15 ], Pd(ptf)2 [ 11 ], Pb(ptf)2
[ 16 ], Liptf [ 17 ] ɢ Hf(ptf)4 [ 18 ]. Ⱦɥɢɧɵ ɫɜɹɡɟɣ Ɉ—ɋ ɢ ɋ—ɋJ ɥɟɠɚɬ ɜ ɢɧɬɟɪɜɚɥɚɯ 1,253(3)—
1,276(4) ɢ 1,354(4)—1,528(4) Å ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ, ɩɪɢɱɟɦ Ɉ—ɋɫɪ ɫɨ ɫɬɨɪɨɧɵ ɮɬɨɪɢɪɨɜɚɧɧɨɝɨ ɡɚɦɟɫɬɢɬɟɥɹ ɧɚ 0,015 Å ɞɥɢɧɧɟɟ,
ɚ ɋ—ɋJɫɪ ɧɚ 0,051 Å ɤɨɪɨɱɟ, ɱɟɦ ɫɨ ɫɬɨɪɨɧɵ ɬɪɟɬ-Bu-ɡɚɦɟɫɬɢɬɟɥɹ. ɏɟɥɚɬɧɵɟ ɰɢɤɥɵ
ɢɦɟɸɬ ɡɧɚɱɢɬɟɥɶɧɵɟ ɩɟɪɟɝɢɛɵ ɩɨ ɥɢɧɢɹɦ
Ɉ...O — 14,4(1), 20,1(1) ɢ 20,7(1)q. ɋɪɟɞɧɢɟ
ɡɧɚɱɟɧɢɹ ɪɚɫɫɬɨɹɧɢɣ ɋ—ɋMɟ ɢ ɋ—F
ɜ ɤɨɧɰɟɜɵɯ ɡɚɦɟɫɬɢɬɟɥɹɯ ɪɚɜɧɵ 1,524(4)
ɢ 1,30(1) Å.
ɍɩɚɤɨɜɤɚ ɦɨɥɟɤɭɥ ɤɨɦɩɥɟɤɫɚ ɜ ɤɪɢɫɬɚɥɥɟ ɜ ɧɚɩɪɚɜɥɟɧɢɢ ɨɫɢ ɏ ɩɨɤɚɡɚɧɚ ɧɚ
ɪɢɫ. 3. ȼ ɫɬɪɭɤɬɭɪɟ ɤɪɚɬɱɚɣɲɢɟ ɪɚɫɫɬɨɹɧɢɹ
ɦɟɠɞɭ ɰɟɧɬɪɚɦɢ ɤɨɦɩɥɟɤɫɨɜ Fe…Fe ɥɟɠɚɬ
ɜ ɢɧɬɟɪɜɚɥɟ 8,477—10,598 Å, ɦɟɠɦɨɥɟɤɭɥɹɪɧɨɟ Ʉɑ = 8. Ʉɪɚɬɱɚɣɲɢɟ ɦɟɠɦɨɥɟɤɭɥɹɪɊɢɫ. 2. ɋɬɪɨɟɧɢɟ ɦɨɥɟɤɭɥɵ Fe(ptf)3
ɄɊɂɋɌȺɅɅɂɑȿɋɄȺə ɂ ɆɈɅȿɄɍɅəɊɇȺə ɋɌɊɍɄɌɍɊȺ C24H30FeF9O6
541
Ɋɢɫ. 3. ɍɩɚɤɨɜɤɚ ɦɨɥɟɤɭɥ ɜɞɨɥɶ ɨɫɢ a
ɧɵɟ ɤɨɧɬɚɤɬɵ F…F, F…Ɉ, F…H ɪɚɜɧɵ
2,78(1), 3,20(1), 2,42(1) Å ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ.
Ⱥɧɚɥɢɡ ɭɩɚɤɨɜɤɢ ɤɨɦɩɥɟɤɫɨɜ ɜ ɫɬɪɭɤɬɭɪɟ ɩɪɨɜɟɞɟɧ ɩɨ ɦɟɬɨɞɢɤɟ ɜɵɞɟɥɟɧɢɹ ɬɪɚɧɫɥɹɰɢɨɧɧɨɣ ɩɨɞɪɟɲɟɬɤɢ [ 19 ]. Ⱦɥɹ ɷɬɨɝɨ ɛɵɥɚ ɪɚɫɫɱɢɬɚɧɚ ɬɟɨɪɟɬɢɱɟɫɤɚɹ ɞɢɮɪɚɤɬɨɝɪɚɦɦɚ. ȼ ɪɚɫɱɟɬ ɧɟ ɜɤɥɸɱɚɥɢɫɶ ɚɬɨɦɵ ɜɨɞɨɪɨɞɚ
ɢ ɮɬɨɪɚ. ȼ ɪɟɡɭɥɶɬɚɬɟ ɛɵɥɢ ɜɵɞɟɥɟɧɵ ɬɪɢ
ɧɚɢɛɨɥɟɟ ɡɚɫɟɥɟɧɧɵɯ ɚɬɨɦɚɦɢ ɠɟɥɟɡɚ ɩɥɨɫɤɨɫɬɢ: (0 1 0), (101) ɢ (002). ȼɟɤɬɨɪɵ ɬɪɚɧɫɥɹɰɢɨɧɧɨɣ ɩɨɞɴɹɱɟɣɤɢ: ak = –b, bk = a, ck =
= –a/2+c/2. Ⱥɬɨɦɵ ɠɟɥɟɡɚ ɫɥɟɞɭɸɬ ɭɡɥɚɦ
ɩɨɞɴɹɱɟɣɤɢ: ak = 9,66, bk = 9,22, ck = 9,14 Å,
Dk = 110,4, Ek = 99,7, Jk = 97,3q. Ɉɪɢɟɧɬɢɪɭɹɫɶ ɧɚ ɫɪɟɞɧɢɟ ɡɧɚɱɟɧɢɹ ɥɢɧɟɣɧɵɯ ɢ ɭɝɥɨɜɵɯ ɩɚɪɚɦɟɬɪɨɜ ak = 9,3(2), Dk = 102(6)q,
ɦɨɠɧɨ ɭɫɥɨɜɧɨ ɫɱɢɬɚɬɶ, ɱɬɨ ɤɨɦɩɥɟɤɫɵ ɫɥɟɞɭɸɬ ɈɐɄ-ɹɱɟɣɤɟ.
Ɉɩɢɪɚɹɫɶ ɧɚ ɫɬɪɭɤɬɭɪɧɵɟ ɞɚɧɧɵɟ, ɩɪɨɜɟɞɟɧ ɪɚɫɱɟɬ ɷɧɟɪɝɢɢ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɦɟɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɦɟɬɨɞɨɦ ɚɬɨɦ-ɚɬɨɦɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ. ɉɚɪɚɦɟɬɪɵ ɩɨɬɟɧɰɢɚɥɨɜ Ȼɭɤɢɧɝɟɦɚ ɞɥɹ ɪɚɫɱɟɬɨɜ ɜɡɹɬɵ ɢɡ ɪɚɛɨɬ Ɂɨɪɤɨɝɨ [ 20 ]. ɉɚɪɚɦɟɬɪɵ ɩɨɬɟɧɰɢɚɥɨɜ ɞɥɹ ɚɬɨɦɚ ɠɟɥɟɡɚ ɪɚɫɫɱɢɬɵɜɚɥɢ ɢɫɯɨɞɹ ɢɡ ɝɥɭɛɢɧɵ ɩɨɬɟɧɰɢɚɥɶɧɨɣ ɹɦɵ, ɪɚɜɧɨɣ 1,15 ɤȾɠ/ɦɨɥɶ, ɢ ɪɚɜɧɨɜɟɫɧɨɝɨ ɪɚɫɫɬɨɹɧɢɹ 3,94 Å. ɗɧɟɪɝɢɸ ɪɚɫɫɱɢɬɵɜɚɥɢ ɩɨ ɮɨɪɦɭɥɟ
N
U
n
n
1/ 2 ¦ ¦ ¦ ª Ai , j / Ri6, j Bi , j ˜ exp(Di , j ˜ Ri , j ) º,
¬
¼
k 2i 1 j 1
ɝɞɟ k — ɧɨɦɟɪ ɫɨɫɟɞɧɟɣ ɦɨɥɟɤɭɥɵ; N — ɱɢɫɥɨ ɦɨɥɟɤɭɥ ɢɡ ɛɥɢɠɚɣɲɟɝɨ ɨɤɪɭɠɟɧɢɹ; i — ɧɨɦɟɪ
ɚɬɨɦɚ ɩɟɪɜɨɣ ɦɨɥɟɤɭɥɵ; j — ɧɨɦɟɪ ɚɬɨɦɚ k-ɣ ɦɨɥɟɤɭɥɵ; n — ɱɢɫɥɨ ɚɬɨɦɨɜ ɜ ɦɨɥɟɤɭɥɟ;
Ri,j — ɪɚɫɫɬɨɹɧɢɟ ɦɟɠɞɭ i ɢ j ɚɬɨɦɚɦɢ; Ai,j, Bi,j, Di,j — ɩɚɪɚɦɟɬɪɵ ɚɬɨɦ-ɚɬɨɦɧɵɯ ɩɨɬɟɧɰɢɚɥɨɜ.
ɉɨɥɭɱɟɧɧɵɟ ɪɚɫɱɟɬɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɩɪɢɜɟɞɟɧɵ ɜ
ɬɚɛɥ. 1. Ⱦɥɹ ɫɨɟɞɢɧɟɧɢɹ Fe(hfa)3, Fe(tfa)3 ɢ Fe(aa)3 ɨɧɢ ɫɨɝɥɚɫɭɸɬɫɹ ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦɢ ɡɧɚɱɟɧɢɹɦɢ ɬɟɩɥɨɬ ɫɭɛɥɢɦɚɰɢɢ, ɚ ɞɥɹ ɤɨɦɩɥɟɤɫɨɜ Fe(ptf)3, Fe(dpm)3 ɢ Fe(dbm)3, ɭ ɤɨɬɨɪɵɯ ɛɨɥɶɲɨɟ ɱɢɫɥɨ ɚɬɨɦɨɜ ɜ ɦɨɥɟɤɭɥɟ, ɪɚɫɱɟɬɧɵɟ ɜɟɥɢɱɢɧɵ ɡɚɜɵɲɟɧɵ. ɇɚ ɨɫɧɨɜɟ ɡɧɚɱɟɧɢɣ ɪɚɫɱɟɬɧɨɣ
ɷɧɟɪɝɢɢ ɦɟɠɦɨɥɟɤɭɥɹɪɧɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɤɨɦɩɥɟɤɫɵ ɦɨɠɧɨ ɪɚɫɩɨɥɨɠɢɬɶ ɜ ɪɹɞ:
Fe(hfa)3 Fe(tfa)3 Fe(aa)3 Fe(ptf)3 Fe(dpm)3 Fe(dbm)3
95,7
107,7
121,1
127,2
142,7
250,6
Ⱥɧɚɥɨɝɢɱɧɵɣ ɪɹɞ ɤɨɦɩɥɟɤɫɨɜ ɦɨɠɧɨ ɡɚɩɢɫɚɬɶ ɢ ɧɚ ɨɫɧɨɜɟ ɬɟɪɦɨɝɪɚɜɢɦɟɬɪɢɱɟɫɤɢɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ɬɟɦɩɟɪɚɬɭɪɵ ɩɨɥɭɢɫɩɚɪɟɧɢɹ (T1/2, qɋ):
Fe(hfa)3 Fe(ptf)3 Fe(tfa)3 Fe(aa)3 Fe(dpm)3 Fe(dbm)3
365
440
445
480
490
640
ɉɨɥɭɱɟɧɧɵɟ ɪɹɞɵ ɬɚɤɠɟ ɯɨɪɨɲɨ ɫɨɝɥɚɫɭɸɬɫɹ ɞɪɭɝ ɫ ɞɪɭɝɨɦ.
ɁȺɄɅɘɑȿɇɂȿ
Ɉɩɢɫɚɧ ɫɢɧɬɟɡ ɥɟɬɭɱɟɝɨ ɤɨɦɩɥɟɤɫɚ ɠɟɥɟɡɚ(III) ɫ ɩɢɜɚɥɨɢɥɬɪɢɮɬɨɪɚɰɟɬɨɧɨɦ ɢ ɩɪɨɜɟɞɟɧɨ
ɟɝɨ ɢɫɫɥɟɞɨɜɚɧɢɟ ɦɟɬɨɞɚɦɢ ɊɋȺ ɢ ɬɟɪɦɨɝɪɚɜɢɦɟɬɪɢɢ. ɍɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɫɬɪɭɤɬɭɪɚ ɞɚɧɧɨɝɨ
ɤɨɦɩɥɟɤɫɚ ɚɧɚɥɨɝɢɱɧɚ ɫɬɪɭɤɬɭɪɚɦ ɞɪɭɝɢɯ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III). ȼɫɟ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɟ
ɤɨɧɬɚɤɬɵ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɵ. Ɋɚɫɱɟɬɧɵɟ ɜɟɥɢɱɢɧɵ ɷɧɟɪɝɢɢ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ
542
ɂ.Ⱥ. ȻȺɃȾɂɇȺ, ɇ.ȼ. ɄɍɊȺɌɖȿȼȺ, ɉ.Ⱥ. ɋɌȺȻɇɂɄɈȼ, ɋ.Ⱥ. ȽɊɈɆɂɅɈȼ
ɞɥɹ E-ɞɢɤɟɬɨɧɚɬɨɜ ɠɟɥɟɡɚ(III) ɧɚɯɨɞɹɬɫɹ ɜ ɯɨɪɨɲɟɦ ɫɨɝɥɚɫɢɢ ɫ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦɢ ɬɟɩɥɨɬɚɦɢ
ɫɭɛɥɢɦɚɰɢɢ ɤɨɦɩɥɟɤɫɨɜ.
Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ ɞɥɹ Fe(ptf)3 ɞɟɩɨɧɢɪɨɜɚɧɵ ɜ Ʉɟɦɛɪɢɞɠɫɤɨɦ ɰɟɧɬɪɟ ɤɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɯ ɞɚɧɧɵɯ ɩɨɞ ɧɨɦɟɪɨɦ CCCDC 600579. Ʉɨɩɢɢ ɞɚɧɧɵɯ ɦɨɠɧɨ ɩɨɥɭɱɢɬɶ ɩɨ
fax:44-1223-336033; e-mail: [email protected] ɢɥɢ www.ccdc.cam.as.uk.
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
1. Fackler J.P. // Progress Inorg. Chem. – 1966. – 7. – P. 361 – 425.
2. Moshier R.V., Sievers R.E. Gas Chromatography of Metal Chelates. – N. Y.: Pergamon Press, 1967.
3. ɂɝɭɦɟɧɨɜ ɂ.Ʉ., ɑɭɦɚɱɟɧɤɨ ɘ.ȼ., Ɂɟɦɫɤɨɜ ɋ.ȼ. ɉɪɨɛɥɟɦɵ ɯɢɦɢɢ ɢ ɩɪɢɦɟɧɟɧɢɹ E-ɞɢɤɟɬɨɧɚɬɨɜ ɦɟɬɚɥɥɨɜ/ ɉɨɞ ɪɟɞ. ȼ.ɂ. ɋɩɢɰɢɧɚ – Ɇ.: ɇɚɭɤɚ, 1982. – C. 100 – 120.
4. ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ., ɋɵɫɨɟɜ ɋ.ȼ., ȼɚɧɢɧɚ ɇ.ɋ. // ɗɥɟɤɬɪɨɧɧɵɣ ɠɭɪɧɚɥ sɂɫɫɥɟɞɨɜɚɧɨ ɜ Ɋɨɫɫɢɢs. –
http://zhurnal. ape. relarn. ru/articles/2001/023. pdf
5. Hu M. L., Jin Z.-M., Miao Q., Fang L.-P. // Z. Kristallogr. – New Cryst. Struct. – 2001. – 216. – P. 597.
6. Pfluger C.E., Haradem P.S. // Inorg. Chim. Acta. – 1983. – 69. – P. 141 – 146.
7. Ȼɚɣɞɢɧɚ ɂ.Ⱥ., ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ. ɢ ɞɪ. // ɀɭɪɧ. cɬɪɭɤɬɭɪ. xɢɦɢɢ. – 1986. – 27, ʋ 3. – C. 102 – 109.
8. Kaitner B., Kamenar B. // Cryst. Struct. Commun. – 1980. – 9. – P. 487 – 492.
9. Ȼɚɣɞɢɧɚ ɂ.Ⱥ., ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ., ɂɝɭɦɟɧɨɜ ɂ.Ʉ., Ȼɨɪɢɫɨɜ ɋ.ȼ. // Ʉɨɨɪɞɢɧɚɰ. xɢɦɢɹ. – 1986. – 12, ʋ 2. –
ɋ. 258 – 265.
10. Ȼɚɣɞɢɧɚ ɂ.Ⱥ., ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ., ɂɝɭɦɟɧɨɜ ɂ.Ʉ., Ȼɨɪɢɫɨɜ ɋ.ȼ. // Ɍɚɦ ɠɟ. – ʋ 3. – ɋ. 404 – 408.
11. Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ɂɚɣɰɟɜɚ ȿ.Ƚ., ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ. ɢ ɞɪ. // Ɍɚɦ ɠɟ. – 1990. – 16, ʋ 5. – ɋ. 693 – 698.
12. Bruker AXS Inc. (2004) SHELXTL (Version 6.12). Bruker Advanced X-Ray Solutions, Madison,
Wisconsin, USA.
13. ɋɬɚɛɧɢɤɨɜ ɉ.Ⱥ., ɂɝɭɦɟɧɨɜ ɂ.Ʉ. // ɂɡɜ. ɋɈ Ⱥɇ ɋɋɋɊ. ɋɟɪ. ɯɢɦ. ɧɚɭɤ. – 1986. – ȼɵɩ. 3. – C. 20 – 22.
14. ɉɨɥɹɧɫɤɚɹ Ɍ.Ɇ., Ɋɨɠɞɟɫɬɜɟɧɫɤɚɹ ɂ.ȼ., Ɇɚɪɬɵɧɨɜɚ Ɍ.ɇ. // ɀɭɪɧ. cɬɪɭɤɬɭɪ. xɢɦɢɢ. – 1993. – 34, ʋ 3.
– C. 96 – 108.
15. DelaRoza M.J., Bander K.K., Higashiya S. et al. // J. Fluorine Chem. – 2003. – 123. – P. 109.
16. Ʉɪɢɫɸɤ ȼ.ȼ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ. ɢ ɞɪ. // ɀɭɪɧ. cɬɪɭɤɬɭɪ. xɢɦɢɢ. – 1994. – 35, ʋ 6. –
C. 197 – 201.
17. Ɏɢɥɚɬɨɜ ȿ.ɋ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., ɂɝɭɦɟɧɨɜ ɂ.Ʉ. // Ɍɚɦ ɠɟ. – 2006. – 47, ʋ 3. – ɋ. 498 – 502.
18. ɀɟɪɢɤɨɜɚ Ʉ.ȼ., Ɇɨɪɨɡɨɜɚ ɇ.Ȼ., ɉɟɪɟɫɵɩɤɢɧɚ ȿ.ȼ. ɢ ɞɪ. // Ɍɚɦ ɠɟ. – C. 581 – 584.
19. Ȼɨɪɢɫɨɜ ɋ.ȼ. // Ɍɚɦ ɠɟ. – 1986. – 27, ʋ 3. – C. 164 – 166.
20. Ɍɢɦɨɮɟɟɜɚ Ɍ.ȼ., ɑɟɪɧɢɤɨɜɚ ɇ.ɘ., Ɂɨɪɤɢɣ ɉ.Ɇ. // ɍɫɩɟɯɢ ɯɢɦɢɢ. – 1980. – XLIX, ȼɵɩ. 6. –
C. 966 – 997.