ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ... Ɇɚɪɬ – ɚɩɪɟɥɶ ɋ. 380 – 384 2006. Ɍɨɦ 47, ʋ 2

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ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ
2006. Ɍɨɦ 47, ʋ 2
Ɇɚɪɬ – ɚɩɪɟɥɶ
ɋ. 380 – 384
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
ɍȾɄ 546.97+548.736
ɋɂɇɌȿɁ ɂ ɋɌɊɍɄɌɍɊȺ ɄɈɆɉɅȿɄɋɇɈȽɈ ɋɈȿȾɂɇȿɇɂə Rh(III) ɋɈɋɌȺȼȺ
(NH4)2[Rh(NO2)3(NH3)(P-OH)]2
© 2006 ɋ . ɉ . ɏ ɪ ɚ ɧ ɟ ɧ ɤ ɨ , ɂ . Ⱥ . Ȼ ɚ ɣ ɞ ɢ ɧ ɚ , ɋ . Ⱥ . Ƚ ɪ ɨ ɦ ɢ ɥ ɨ ɜ *
ɂɧɫɬɢɬɭɬ ɧɟɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɢɦ. Ⱥ.ȼ. ɇɢɤɨɥɚɟɜɚ ɋɈ ɊȺɇ, ɇɨɜɨɫɢɛɢɪɫɤ
ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 16 ɦɚɹ 2005 ɝ.
Ɉɩɪɟɞɟɥɟɧɚ ɤɪɢɫɬɚɥɥɢɱɟɫɤɚɹ ɫɬɪɭɤɬɭɪɚ ɧɨɜɨɝɨ ɫɨɟɞɢɧɟɧɢɹ Rh(III) ɫɨɫɬɚɜɚ
(NH4)2[Rh(NO2)3(NH3)(P-OH)]2. Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ H16N10O14Rh2:
a = 6,3963(2), b = 9,3701(4), c = 13,6646(5) Å, E = 102,266(1)°, V = 800,28(5) Å3, Z = 2,
dɜɵɱ = 2,432 ɝ/cɦ3. Ɋɚɫɫɬɨɹɧɢɟ Rh…Rh ɜ ɞɢɦɟɪɟ 3,200 Å.
Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ: ɪɨɞɢɣ, ɪɟɧɬɝɟɧɨɮɚɡɨɜɵɣ ɚɧɚɥɢɡ, ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɵɣ ɚɧɚɥɢɡ,
ɤɪɢɫɬɚɥɥɨɯɢɦɢɹ.
ȼ ɧɚɫɬɨɹɳɟɣ ɪɚɛɨɬɟ ɫɢɧɬɟɡɢɪɨɜɚɧ ɢ ɢɫɫɥɟɞɨɜɚɧ ɞɢɦɟɪɧɵɣ ɤɨɦɩɥɟɤɫ ɪɨɞɢɹ(III) ɫɨɫɬɚɜɚ
(NH4)2[Rh(NO2)3OH(NH3)]2. Ɋɚɧɟɟ ɧɚɦɢ ɛɵɥɢ ɜɵɞɟɥɟɧɵ ɢ ɢɡɭɱɟɧɵ ɦɟɬɨɞɨɦ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɚɧɚɥɢɡɚ ɞɜɟ ɦɨɞɢɮɢɤɚɰɢɢ ɬɪɢɧɢɬɪɨɬɪɢɚɦɦɢɧɪɨɞɢɹ(III) — D [ 1 ] ɢ E [ 2 ]. ȼ ɦɟɬɨɞɢɤɟ ɩɨɥɭɱɟɧɢɹ D-ɦɨɞɢɮɢɤɚɰɢɢ ɬɪɢɧɢɬɪɨɬɪɢɚɦɦɢɧɚ Rh(III) ɛɵɥɚ ɢɫɩɨɥɶɡɨɜɚɧɚ ɪɟɚɤɰɢɹ ɞɟɧɢɬɪɚɰɢɢ
ɝɟɤɫɚɧɢɬɪɨɪɨɞɢɚɬɚ ɧɚɬɪɢɹ ɫɭɥɶɮɚɦɢɧɨɜɨɣ ɤɢɫɥɨɬɨɣ. ɗɬɚ ɪɟɚɤɰɢɹ ɩɨɡɜɨɥɹɟɬ ɩɨɥɭɱɢɬɶ ɜ ɪɚɫɬɜɨɪɟ ɬɪɢɧɢɬɪɨɬɪɢɚɤɜɚɤɨɦɩɥɟɤɫ Rh(III), ɨɛɥɚɞɚɸɳɢɣ ɜɵɫɨɤɨɣ ɪɟɚɤɰɢɨɧɧɨɣ ɫɩɨɫɨɛɧɨɫɬɶɸ ɤ ɪɟɚɤɰɢɹɦ ɡɚɦɟɳɟɧɢɹ. ȼɜɟɞɟɧɢɟ ɜ ɬɚɤɨɣ ɪɚɫɬɜɨɪ ɢɡɛɵɬɤɚ ɚɦɦɢɚɤɚ ɩɪɢɜɨɞɢɬ ɤ ɨɛɪɚɡɨɜɚɧɢɸ ɬɪɭɞɧɨɪɚɫɬɜɨɪɢɦɨɝɨ [Rh(NO2)3(NH3)3]. ȼ ɞɚɧɧɨɣ ɪɚɛɨɬɟ ɦɵ ɢɡɦɟɧɢɥɢ ɭɫɥɨɜɢɹ ɫɢɧɬɟɡɚ ɬɚɤ, ɱɬɨɛɵ ɩɪɢ
ɞɚɥɶɧɟɣɲɟɦ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡɨɜɚɧɢɢ ɫɨɯɪɚɧɢɬɶ ɜɨ ɜɧɭɬɪɟɧɧɟɣ ɫɮɟɪɟ ɬɪɢɧɢɬɪɨɬɪɢɚɤɜɚɤɨɦɩɥɟɤɫɚ
ɤɨɨɪɞɢɧɚɰɢɸ ɯɨɬɹ ɛɵ ɨɞɧɨɣ ɦɨɥɟɤɭɥɵ ɜɨɞɵ.
ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɱɚɫɬɶ. ɇɚ ɩɟɪɜɨɧɚɱɚɥɶɧɨɦ ɷɬɚɩɟ ɦɟɬɨɞɢɤɚ ɫɢɧɬɟɡɚ ɚɧɚɥɨɝɢɱɧɚ ɨɩɢɫɚɧɧɨɣ ɪɚɧɟɟ [ 1 ]. 0,5 ɦɦɨɥɹ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɝɨ Na3[Rh(NO2)6] ɪɚɫɬɜɨɪɹɥɢ ɜ 5 ɦɥ 1,0 Ɇ ɚɡɨɬɧɨɣ
ɤɢɫɥɨɬɵ. Ɂɚɬɟɦ ɜ ɪɚɫɬɜɨɪ ɱɚɫɬɹɦɢ, ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɨ, ɞɥɹ ɩɪɟɞɨɬɜɪɚɳɟɧɢɹ ɛɭɪɧɨɝɨ ɝɚɡɨɜɵɞɟɥɟɧɢɹ ɜɧɨɫɢɥɢ 0,145 ɝ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɭɥɶɮɚɦɢɧɨɜɨɣ ɤɢɫɥɨɬɵ. Ɋɟɚɤɰɢɨɧɧɭɸ ɫɦɟɫɶ ɜɵɞɟɪɠɢɜɚɥɢ ɜ ɩɪɟɞɟɥɚɯ ɩɨɥɭɱɚɫɚ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɞɨ ɭɝɚɫɚɧɢɹ ɝɚɡɨɜɵɞɟɥɟɧɢɹ, ɩɨɫɥɟ ɱɟɝɨ
ɩɟɪɟɧɨɫɢɥɢ ɧɚ ɜɨɞɹɧɭɸ ɛɚɧɸ ɫ ɬɟɦɩɟɪɚɬɭɪɨɣ 50 qC ɢ ɧɚɝɪɟɜɚɥɢ 30 ɦɢɧ. Ɂɚɬɟɦ, ɧɟ ɭɛɢɪɚɹ ɪɚɫɬɜɨɪɚ ɫ ɛɚɧɢ, ɜɧɨɫɢɥɢ ɜ ɧɟɝɨ ɩɨɫɬɟɩɟɧɧɨ ɩɨ ɤɚɩɥɹɦ ɪɚɡɛɚɜɥɟɧɧɵɣ ɜɨɞɨɣ ɚɦɦɢɚɤ (1:4) ɞɨ ɪɇ 7.
ȼ ɩɪɨɰɟɫɫɟ ɧɚɝɪɟɜɚɧɢɹ ɫɬɪɨɝɨ ɤɨɧɬɪɨɥɢɪɨɜɚɥɢ ɪɇ, ɭɞɟɪɠɢɜɚɹ ɩɨɫɬɨɹɧɧɭɸ ɜɟɥɢɱɢɧɭ 7 ɛɟɡ ɩɪɟɜɵɲɟɧɢɹ ɢ ɩɨɧɢɠɟɧɢɹ ɟɟ ɞɨɛɚɜɥɟɧɢɟɦ ɪɚɫɬɜɨɪɚ ɚɦɦɢɚɤɚ. ɉɪɢ 50 qC ɪɚɫɬɜɨɪ ɜɵɞɟɪɠɢɜɚɥɢ
ɜ ɬɟɱɟɧɢɟ ɱɚɫɚ, ɡɚɬɟɦ ɩɨɞɧɢɦɚɥɢ ɬɟɦɩɟɪɚɬɭɪɭ ɞɨ 90 qC, ɭɩɚɪɢɜɚɥɢ ɪɚɫɬɜɨɪ ɜɞɜɨɟ ɢ ɭɛɢɪɚɥɢ ɟɝɨ
ɫ ɛɚɧɢ. ɉɪɢ ɨɯɥɚɠɞɟɧɢɢ ɪɚɫɬɜɨɪɚ ɞɨ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɵ ɜɵɞɟɥɹɥɫɹ ɛɟɫɰɜɟɬɧɵɣ ɤɪɢɫɬɚɥɥɢɱɟɫɤɢɣ ɨɫɚɞɨɤ ɜ ɜɢɞɟ ɢɝɥ, ɤɨɥɢɱɟɫɬɜɨ ɤɨɬɨɪɨɝɨ ɭɜɟɥɢɱɢɜɚɥɨɫɶ ɩɨ ɦɟɪɟ ɢɫɩɚɪɟɧɢɹ ɠɢɞɤɨɣ
ɮɚɡɵ. Ɉɫɚɞɨɤ ɨɬɞɟɥɹɥɢ ɨɬ ɪɚɫɬɜɨɪɚ ɧɚ ɫɬɟɤɥɹɧɧɨɦ ɮɢɥɶɬɪɟ, ɩɪɨɦɵɜɚɥɢ ɜɨɞɧɨ-ɫɩɢɪɬɨɜɨɣ ɫɦɟɫɶɸ (1:2) ɢ ɜɵɫɭɲɢɜɚɥɢ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ ɧɚ ɜɨɡɞɭɯɟ.
ɂɄ ɫɩɟɤɬɪ ɡɚɩɢɫɵɜɚɥɢ ɧɚ ɩɪɢɛɨɪɟ SCIMITAR FTS2000 ɜ ɬɚɛɥɟɬɤɚɯ KBr. Ɋɟɧɬɝɟɧɞɢɮɪɚɤɬɨɦɟɬɪɢɱɟɫɤɨɟ ɢɫɫɥɟɞɨɜɚɧɢɟ ɩɪɨɜɟɞɟɧɨ ɧɚ ɞɢɮɪɚɤɬɨɦɟɬɪɟ ȾɊɈɇ-SEIFERT-RM4 (CuKD-ɢɡɥɭɱɟɧɢɟ, Ni-ɮɢɥɶɬɪ, ɞɟɬɟɤɬɨɪ ɫɰɢɧɬɢɥɥɹɰɢɨɧɧɵɣ ɫ ɚɦɩɥɢɬɭɞɧɨɣ ɞɢɫɤɪɢɦɢɧɚɰɢɟɣ) ɜ ɨɛɥɚɫɬɢ ɭɝɥɨɜ
2T ɨɬ 5 ɞɨ 70q, ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. Ɉɛɪɚɡɟɰ (ɩɨɫɥɟ ɢɫɬɢɪɚɧɢɹ ɤɪɢɫɬɚɥɥɨɜ ɜ ɫɬɭɩɤɟ
* E-mail: [email protected]ɫhe.nsk.su
381
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɍɚɛɥɢɰɚ 1
Ʉɨɨɪɞɢɧɚɬɵ ɛɚɡɢɫɧɵɯ ɚɬɨɦɨɜ ɢ ɢɡɨɬɪɨɩɧɵɟ ɬɟɩɥɨɜɵɟ ɮɚɤɬɨɪɵ
Ⱥɬɨɦ
x/a
y/b
z/c
Uɷɤɜ
Ⱥɬɨɦ
x/a
Rh(1)
O(1)
N(1)
N(2)
N(3)
O(11)
O(12)
0,93528(4)
0,8234(5)
0,6758(6)
1,0790(7)
0,7835(6)
0,6115(6)
0,5647(8)
0,84110(3)
1,0100(3)
0,7232(4)
0,6916(4)
0,9141(4)
0,7197(4)
0,6698(6)
0,02455(2)
–0,0705(2)
–0,0293(3)
0,1187(3)
0,1288(3)
–0,1198(3)
0,0241(4)
0,02165(14)
0,0246(6)
0,0356(8)
0,0403(9)
0,0349(8)
0,0458(8)
0,0820(17)
O(21)
O(22)
O(31)
O(32)
N(4)
N(5)
1,0178(16)
1,2325(7)
0,6424(6)
0,8083(13)
1,0776(8)
0,6000(8)
y/b
z/c
Uɷɤɜ
0,5751(6) 0,1184(7) 0,195(5)
0,7237(5) 0,1822(4) 0,0784(15)
1,0058(4) 0,1073(3) 0,0508(9)
0,8617(8) 0,2108(4) 0,129(3)
0,7514(6) –0,0847(3) 0,0368(9)
0,9709(5) –0,2760(3) 0,0378(9)
Ɍɚɛɥɢɰɚ 2
Ɉɫɧɨɜɧɵɟ ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ d, Å ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ Z, ɝɪɚɞ.
Ɋɚɫɫɬɨɹɧɢɟ
d
ɍɝɨɥ
Z
Rh(1)—N(2)
Rh(1)—N(1)
Rh(1)—N(3)
Rh(1)—O(1)
Rh(1)—O(1)#1
Rh(1)—N(4)
Rh(1)—Rh(1)#1
O(1)—Rh(1)#1
N(1)—O(11)
N(1)—O(12)
N(2)—O(21)
N(2)—O(22)
N(3)—O(32)
N(3)—O(31)
1,990(4)
1,999(4)
2,007(4)
2,076(3)
2,077(3)
2,083(4)
3,1998(6)
2,077(3)
1,219(5)
1,227(6)
1,160(7)
1,203(6)
1,202(6)
1,236(5)
N(2)—Rh(1)—N(1)
N(2)—Rh(1)—N(3)
N(1)—Rh(1)—N(3)
N(2)—Rh(1)—O(1)
N(1)—Rh(1)—O(1)
N(3)—Rh(1)—O(1)
N(2)—Rh(1)—O(1)#1
N(1)—Rh(1)—O(1)#1
N(3)—Rh(1)—O(1)#1
O(1)—Rh(1)—O(1)#1
94,72(16)
90,44(17)
87,73(16)
172,62(15)
92,42(14)
91,72(14)
93,77(15)
171,18(14)
89,82(14)
79,18(11)
ɍɝɨɥ
Z
N(2)—Rh(1)—N(4)
88,1(2)
N(1)—Rh(1)—N(4)
88,21(18)
N(3)—Rh(1)—N(4)
175,56(18)
O(1)—Rh(1)—N(4)
90,23(17)
O(1)#1—Rh(1)—N(4)
94,46(17)
Rh(1)—O(1)—Rh(1)#1 100,82(11)
O(11)—N(1)—O(12)
118,6(4)
O(21)—N(2)—O(22)
117,5(5)
O(32)—N(3)—O(31)
116,8(4)
#1 –x+2, –y+2, –z.
ɫ ɝɟɩɬɚɧɨɦ) ɛɵɥ ɩɪɢɝɨɬɨɜɥɟɧ ɜ ɜɢɞɟ ɬɨɧɤɨɝɨ ɫɥɨɹ ɧɚ ɩɨɥɢɪɨɜɚɧɧɨɣ ɫɬɨɪɨɧɟ ɫɬɚɧɞɚɪɬɧɨɣ ɤɜɚɪɰɟɜɨɣ ɤɸɜɟɬɵ. ȼ ɤɚɱɟɫɬɜɟ ɜɧɟɲɧɟɝɨ ɷɬɚɥɨɧɚ ɢɫɩɨɥɶɡɨɜɚɥɢ ɨɛɪɚɡɟɰ ɩɨɥɢɤɪɢɫɬɚɥɥɢɱɟɫɤɨɝɨ
ɤɪɟɦɧɢɹ (ɚ = 5,4309, O = 1,540562 Å), ɩɪɢɝɨɬɨɜɥɟɧɧɵɣ ɚɧɚɥɨɝɢɱɧɨ. ɉɨɥɭɱɟɧɧɚɹ ɞɢɮɪɚɤɬɨɝɪɚɦɦɚ ɩɨɥɧɨɫɬɶɸ ɢɧɞɢɰɢɪɭɟɬɫɹ ɩɨ ɞɚɧɧɵɦ ɢɫɫɥɟɞɨɜɚɧɢɹ ɨɬɨɛɪɚɧɧɨɝɨ ɦɨɧɨɤɪɢɫɬɚɥɥɚ.
ɂɫɫɥɟɞɨɜɚɧɢɟ ɦɨɧɨɤɪɢɫɬɚɥɥɚ ɩɪɨɜɟɞɟɧɨ ɧɚ ɚɜɬɨɦɚɬɢɱɟɫɤɨɦ ɞɢɮɪɚɤɬɨɦɟɬɪɟ X8 APEX
BRUKER (MoKD-ɢɡɥɭɱɟɧɢɟ, ɝɪɚɮɢɬɨɜɵɣ ɦɨɧɨɯɪɨɦɚɬɨɪ, ɨɛɥɚɫɬɶ ɭɝɥɨɜ T ɨɬ 3 ɞɨ 30°, 5844 ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢ 1823 ɧɟɡɚɜɢɫɢɦɵɯ ɨɬɪɚɠɟɧɢɹ). Ʉɪɢɫɬɚɥɥɨɝɪɚɮɢɱɟɫɤɢɟ ɞɚɧɧɵɟ H16N10O14Rh2:
a = 6,3963(2), b = 9,3701(4), c = 13,6646(5) Å, E = 102,266(1)°, ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɚɹ ɝɪɭɩɩɚ Ɋ21/ɫ,
V = 800,28(5) Å3, Z = 2, dɜɵɱ = 2,432 ɝ/cɦ3. ɋɬɪɭɤɬɭɪɚ ɪɟɲɟɧɚ ɦɟɬɨɞɨɦ ɬɹɠɟɥɨɝɨ ɚɬɨɦɚ ɢ ɭɬɨɱɧɟɧɚ
ɜ ɚɧɢɡɨɬɪɨɩɧɨɦ (ɞɥɹ ɚɬɨɦɨɜ ɜɨɞɨɪɨɞɚ — ɢɡɨɬɪɨɩɧɨɦ) ɩɪɢɛɥɢɠɟɧɢɢ. Ⱥɬɨɦɵ ɜɨɞɨɪɨɞɚ ɱɚɫɬɢɱɧɨ
ɥɨɤɚɥɢɡɨɜɚɧɵ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨ, ɚ ɱɚɫɬɢɱɧɨ ɡɚɞɚɧɵ ɝɟɨɦɟɬɪɢɱɟɫɤɢ ɜ ɢɞɟɚɥɢɡɢɪɨɜɚɧɧɵɯ ɩɨɡɢɰɢɹɯ. ɉɪɢ ɨɤɨɧɱɚɬɟɥɶɧɨɦ ɩɨɥɧɨɦɚɬɪɢɱɧɨɦ ɭɬɨɱɧɟɧɢɢ 151 ɫɬɪɭɤɬɭɪɧɨɝɨ ɩɚɪɚɦɟɬɪɚ ɡɧɚɱɟɧɢɹ
ɮɚɤɬɨɪɨɜ ɪɚɫɯɨɞɢɦɨɫɬɢ ɫɨɫɬɚɜɢɥɢ R1 = 0,0352, wR2 = 0,0862, ɞɥɹ ɨɬɪɚɠɟɧɢɣ ɫ I t 2V(I )
R1 = 0,0321, wR2 = 0,0849, S-ɮɚɤɬɨɪ ɩɨ F 2 1,090, ɤɨɷɮɮɢɰɢɟɧɬ ɷɤɫɬɢɧɤɰɢɢ 0,0000(7). ȼɫɟ ɪɚɫɱɟɬɵ ɜɵɩɨɥɧɟɧɵ ɩɨ ɤɨɦɩɥɟɤɫɭ ɩɪɨɝɪɚɦɦ SHELX-97 [ 3 ]. Ʉɨɨɪɞɢɧɚɬɵ ɛɚɡɢɫɧɵɯ ɚɬɨɦɨɜ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥ. 1, ɦɟɠɚɬɨɦɧɵɟ ɪɚɫɫɬɨɹɧɢɹ ɢ ɜɚɥɟɧɬɧɵɟ ɭɝɥɵ — ɜ ɬɚɛɥ. 2.
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Ɉɩɢɫɚɧɢɟ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɵ. ɋɬɪɭɤɬɭɪɧɵɦɢ ɟɞɢɧɢɰɚɦɢ ɢɫɫɥɟɞɨɜɚɧɧɨɝɨ ɫɨɟɞɢɧɟɧɢɹ ɹɜɥɹɸɬɫɹ ɞɢɦɟɪɧɵɟ ɤɨɦɩɥɟɤɫɧɵɟ ɚɧɢɨɧɵ ɫɨɫɬɚɜɚ [Rh(NO2)3(NH3)(OH)] 22 ɢ ɤɚɬɢɨɧɵ
ɚɦɦɨɧɢɹ. ȼ ɂɄ ɫɩɟɤɬɪɟ ɜɵɞɟɥɟɧɧɨɝɨ ɤɨɦɩɥɟɤɫɚ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɬɪɢɧɢɬɪɨɬɪɢɚɦɦɢɧɪɨɞɢɟɦ(III)
ɧɚɛɥɸɞɚɸɬɫɹ ɡɧɚɱɢɬɟɥɶɧɵɟ ɢɡɦɟɧɟɧɢɹ ɜ ɨɛɥɚɫɬɢ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ ɫɜɹɡɟɣ N—H- ɢ O—Hɝɪɭɩɩ. ȼ ɨɛɥɚɫɬɢ ɜɚɥɟɧɬɧɵɯ ɤɨɥɟɛɚɧɢɣ ɫɜɹɡɢ O—ɇ ɧɚɛɥɸɞɚɟɬɫɹ ɧɨɜɚɹ ɭɡɤɚɹ ɫɢɦɦɟɬɪɢɱɧɚɹ ɩɨɥɨɫɚ ɫ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ 3471 ɫɦ–1. ȼ ɨɛɥɚɫɬɢ ɤɨɥɟɛɚɧɢɣ N—H ɧɚɛɥɸɞɚɟɬɫɹ ɭɲɢɪɟɧɢɟ ɩɨɥɨɫ
ɢ ɩɨɹɜɥɟɧɢɟ ɧɨɜɨɝɨ ɦɚɤɫɢɦɭɦɚ ɜ ɜɢɞɟ ɩɥɟɱɚ ɩɪɢ a3025 ɫɦ–1, ɫɨɨɬɜɟɬɫɬɜɭɸɳɟɝɨ ɩɨ ɩɨɥɨɠɟɧɢɸ
ɤɨɥɟɛɚɧɢɹɦ ɫɜɹɡɢ N—H ɜ ɢɨɧɟ ɚɦɦɨɧɢɹ [ 4 ]. ȼ ɨɛɥɚɫɬɢ ɜɵɪɨɠɞɟɧɧɵɯ ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ ɫɜɹɡɢ N—H, ɫɜɨɣɫɬɜɟɧɧɵɯ ɤɨɨɪɞɢɧɢɪɨɜɚɧɧɨɣ NH3-ɝɪɭɩɩɟ, ɩɨɦɢɦɨ ɩɨɥɨɫɵ ɩɪɢ 1632 ɫɦ–1,
ɩɪɨɹɜɥɹɟɬɫɹ ɩɨɥɨɫɚ ɧɟɛɨɥɶɲɨɣ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɫ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ 1684 ɫɦ–1, ɯɚɪɚɤɬɟɪɧɚɹ ɞɥɹ
ɢɨɧɚ ɚɦɦɨɧɢɹ. Ɉɞɧɨɜɪɟɦɟɧɧɨ ɫ ɷɬɢɦɢ ɢɡɦɟɧɟɧɢɹɦɢ ɩɨɹɜɥɹɟɬɫɹ ɩɨɥɨɫɚ ɜ ɨɛɥɚɫɬɢ ɩɨɝɥɨɳɟɧɢɹ
ɞɟɮɨɪɦɚɰɢɨɧɧɵɯ ɤɨɥɟɛɚɧɢɣ ɫɜɹɡɢ Rh—OH ɫ ɦɚɤɫɢɦɭɦɨɦ ɩɪɢ 954 ɫɦ–1 [ 4 ]. Ʉɪɨɦɟ ɬɨɝɨ, ɜ ɤɨɦɩɥɟɤɫɟ ɩɪɨɹɜɥɹɸɬɫɹ ɤɨɥɟɛɚɧɢɹ ɤɨɨɪɞɢɧɢɪɨɜɚɧɧɵɯ ɧɢɬɪɨ- ɢ ɚɦɦɢɧɨɝɪɭɩɩ.
ɇɚ ɪɢɫ. 1 ɩɨɤɚɡɚɧɨ ɫɬɪɨɟɧɢɟ ɰɟɧɬɪɨɫɢɦɦɟɬɪɢɱɧɨɝɨ ɤɨɦɩɥɟɤɫɧɨɝɨ ɞɢɦɟɪɚ ɪɨɞɢɹ ɫ ɧɭɦɟɪɚɰɢɟɣ ɚɬɨɦɨɜ ɢ ɷɥɥɢɩɫɨɢɞɚɦɢ ɬɟɩɥɨɜɵɯ ɤɨɥɟɛɚɧɢɣ. Ʉɚɠɞɵɣ ɚɬɨɦ Rh ɢɦɟɟɬ ɫɥɚɛɨ ɢɫɤɚɠɟɧɧɭɸ
ɨɤɬɚɷɞɪɢɱɟɫɤɭɸ ɤɨɨɪɞɢɧɚɰɢɸ, ɨɛɪɚɡɨɜɚɧɧɭɸ ɬɪɟɦɹ ɚɬɨɦɚɦɢ ɚɡɨɬɚ ɧɢɬɪɨɝɪɭɩɩ, ɦɨɥɟɤɭɥɨɣ ɚɦɦɢɚɤɚ ɢ ɞɜɭɦɹ ɝɢɞɪɨɤɫɨɝɪɭɩɩɚɦɢ. Ɍɪɢ ɧɢɬɪɨɝɪɭɩɩɵ ɧɚɯɨɞɹɬɫɹ ɜ ɰɢɫ-ɩɨɥɨɠɟɧɢɢ, ɢɯ ɚɬɨɦɵ ɚɡɨɬɚ ɨɛɪɚɡɭɸɬ ɨɞɧɭ ɢɡ ɝɪɚɧɟɣ ɨɤɬɚɷɞɪɚ. Ⱦɜɟ ɝɢɞɪɨɤɫɢɥɶɧɵɟ ɝɪɭɩɩɵ ɢɝɪɚɸɬ ɪɨɥɶ ɦɨɫɬɢɤɨɜ, ɫɜɹɡɵɜɚɹ ɨɤɬɚɷɞɪɵ Rh ɜ ɰɟɧɬɪɨɫɢɦɦɟɬɪɢɱɧɵɣ ɞɢɦɟɪ ɫ ɪɚɫɫɬɨɹɧɢɟɦ Rh…Rh 3,200 Å, ɜɟɥɢɱɢɧɚ ɭɝɥɚ
Rh—O—Rh ɫɨɫɬɚɜɥɹɟɬ 100,8q. ɋɪɟɞɧɟɟ ɡɧɚɱɟɧɢɟ ɪɚɫɫɬɨɹɧɢɣ Rh—N(NO2) ɪɚɜɧɨ 1,999 Å, ɱɬɨ
ɧɟɫɤɨɥɶɤɨ ɦɟɧɶɲɟ ɧɚɣɞɟɧɧɵɯ ɜ ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɧɢɬɪɨɤɨɦɩɥɟɤɫɚɯ Rh(III): Na3[Rh(NO2)6] [ 5 ],
K3[Rh(NO2)2,5Cl3,5]H2O [ 6 ], K[Rh(NO2)4(NH3)2] [ 7 ], Li3[Rh(NO2)6]4H2O [ 8 ], D-Rh(NO2)3(NH3)3
[ 1 ] ɢ E-Rh(NO2)3(NH3)3 [ 2 ] — 2,056, 2,05, 2,075, 2,04, 2,072 ɢ 2,028 Å ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. Ⱦɥɢɧɚ
ɫɜɹɡɢ Rh—N(NH3) — 2,083 Å, ɝɢɞɪɨɤɫɨɝɪɭɩɩɚ ɧɚɯɨɞɢɬɫɹ ɨɬ ɞɜɭɯ ɚɬɨɦɨɜ Rh ɧɚ ɩɪɚɤɬɢɱɟɫɤɢ
ɪɚɜɧɵɯ ɪɚɫɫɬɨɹɧɢɹɯ Rh—O(OH) 2,076 Å. ȼɚɥɟɧɬɧɵɣ ɭɝɨɥ O—Rh—O ɨɬɤɥɨɧɹɟɬɫɹ ɨɬ ɩɪɹɦɨɝɨ ɧɚ
10,8q. ɋɪɟɞɧɢɟ ɝɟɨɦɟɬɪɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ ɞɥɹ NO2-ɝɪɭɩɩ: ɞɥɢɧɚ ɫɜɹɡɢ N—O 1,208 Å, ɜɚɥɟɧɬɧɵɣ ɭɝɨɥ ONO 117,6q.
ɉɪɨɟɤɰɢɹ ɫɬɪɭɤɬɭɪɵ ɜɞɨɥɶ ɧɚɩɪɚɜɥɟɧɢɹ ɏ ɩɪɢɜɟɞɟɧɚ ɧɚ ɪɢɫ. 2. Ʉɨɦɩɥɟɤɫɧɵɟ ɚɧɢɨɧɵ ɢ ɤɚɬɢɨɧɵ ɫɜɹɡɚɧɵ ɜ ɫɬɪɭɤɬɭɪɟ ɜɨɞɨɪɨɞɧɵɦɢ ɫɜɹɡɹɦɢ ɬɢɩɚ N—H…O, ɜ ɤɨɬɨɪɵɯ ɭɱɚɫɬɜɭɸɬ ɜɫɟ
Ɋɢɫ. 1. ɋɬɪɨɟɧɢɟ ɤɨɦɩɥɟɤɫɧɨɝɨ ɚɧɢɨɧɚ [Rh(NO2)3(NH3)(P-OH)] 22 ɢ ɤɚɬɢɨɧɚ NH 4
ɄɊȺɌɄɂȿ ɋɈɈȻɓȿɇɂə
Ɋɢɫ. 2. ɉɪɨɟɤɰɢɹ ɫɬɪɭɤɬɭɪɵ (NH4)2[Rh(NO2)3(NH3)(P-OH)]2 ɜɞɨɥɶ ɧɚɩɪɚɜɥɟɧɢɹ ɏ
Ɋɢɫ. 3. ɉɫɟɜɞɨɝɟɤɫɚɝɨɧɚɥɶɧɵɣ ɫɥɨɣ ɞɢɦɟɪɨɜ [Rh(NO2)3(NH3)(OH)] 22
ɜ ɤɪɢɫɬɚɥɥɢɱɟɫɤɨɣ ɫɬɪɭɤɬɭɪɟ (NH4)2[Rh(NO2)3(NH3)(P-OH)]2 ɜ ɧɚɩɪɚɜɥɟɧɢɢ [1 0 0]
383
384
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ɚɬɨɦɵ ɜɨɞɨɪɨɞɚ ɤɚɬɢɨɧɚ ɚɦɦɨɧɢɹ. Ʉɪɚɬɱɚɣɲɚɹ ɢɡ ɧɢɯ ɫ ɝɢɞɪɨɤɫɨɝɪɭɩɩɨɣ ɞɢɦɟɪɧɨɝɨ ɚɧɢɨɧɚ
ɢɦɟɟɬ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ 0,92, 1,99, 2,89 Å, 165,3q. Ʉɪɚɬɱɚɣɲɢɟ ɪɚɫɫɬɨɹɧɢɹ ɨɬ ɚɬɨɦɚ Rh ɞɨ ɚɬɨɦɨɜ
ɚɡɨɬɚ, ɩɪɢɧɚɞɥɟɠɚɳɢɯ ɤɚɬɢɨɧɚɦ NH 4 , ɧɚɯɨɞɹɬɫɹ ɜ ɢɧɬɟɪɜɚɥɟ 4,38—4,80 Å.
Ɉɛɳɢɣ ɦɨɬɢɜ ɜɡɚɢɦɧɨɝɨ ɪɚɫɩɨɥɨɠɟɧɢɹ ɞɢɦɟɪɨɜ [Rh(NO2)3(NH3)(OH)] 22 ɛɵɥ ɨɩɪɟɞɟɥɟɧ ɩɨ
ɦɟɬɨɞɢɤɟ ɜɵɞɟɥɟɧɢɹ ɬɪɚɧɫɥɹɰɢɨɧɧɨɣ ɩɨɞɪɟɲɟɬɤɢ [ 9 ]. Ɏɨɪɦɭɥɶɧɚɹ ɟɞɢɧɢɰɚ ɫɨɞɟɪɠɢɬ ɞɜɚ ɬɹɠɟɥɵɯ ɚɬɨɦɚ, ɩɨɷɬɨɦɭ ɭɡɥɚɦ ɩɨɞɪɟɲɟɬɤɢ ɞɨɥɠɧɵ ɫɥɟɞɨɜɚɬɶ ɰɟɧɬɪɵ ɬɹɠɟɫɬɢ ɞɢɦɟɪɨɜ. ɇɚ ɞɢɮɪɚɤɬɨɝɪɚɦɦɟ ɫɪɟɞɢ ɧɚɢɛɨɥɟɟ ɫɢɥɶɧɵɯ ɨɬɪɚɠɟɧɢɣ ɛɵɥɢ ɜɵɛɪɚɧɵ ɬɪɢ — ɫ ɢɧɞɟɤɫɚɦɢ hkl, ɨɛɪɚɡɭɸɳɢɦɢ ɦɚɬɪɢɰɭ ɫ ɞɟɬɟɪɦɢɧɚɧɬɨɦ, ɪɚɜɧɵɦ ɱɢɫɥɭ ɮɨɪɦɭɥɶɧɵɯ ɟɞɢɧɢɰ ɜ ɷɥɟɦɟɧɬɚɪɧɨɣ ɹɱɟɣɤɟ
Z = 2. ɂɫɤɨɦɚɹ ɩɨɞɪɟɲɟɬɤɚ ɦɨɠɟɬ ɛɵɬɶ ɨɩɢɫɚɧɚ ɤɚɤ ɩɟɪɟɫɟɱɟɧɢɟ ɫɟɦɟɣɫɬɜ ɩɥɨɫɤɨɫɬɟɣ (0 1 1),
(0 –1 1) ɢ (1 0 0). Ɉɧɚ ɩɨɫɬɪɨɟɧɚ ɧɚ ɜɟɤɬɨɪɚɯ aɤ = b/2 + ɫ/2, bɤ = –b/2 + ɫ/2, cɤ = ɚ. Ɂɧɚɱɟɧɢɹ ɩɚɪɚɦɟɬɪɨɜ ɩɨɞɴɹɱɟɣɤɢ (aɤ = bɤ = 8,28, cɤ = 6,40 Å, Dɤ = Eɤ = 100,1, Jɤ = 68,9q) ɩɨɤɚɡɵɜɚɸɬ, ɱɬɨ ɜ
ɫɬɪɭɤɬɭɪɟ ɜ ɧɚɩɪɚɜɥɟɧɢɢ X ɦɨɠɧɨ ɜɵɞɟɥɢɬɶ ɩɫɟɜɞɨɝɟɤɫɚɝɨɧɚɥɶɧɵɟ ɫɥɨɢ (ɪɢɫ. 3).
Ⱥɜɬɨɪɵ ɜɵɪɚɠɚɸɬ ɫɜɨɸ ɛɥɚɝɨɞɚɪɧɨɫɬɶ ɤ.ɯ.ɧ. Ⱦ.ɘ. ɇɚɭɦɨɜɭ ɡɚ ɩɪɨɜɟɞɟɧɢɟ ɪɟɧɬɝɟɧɨɫɬɪɭɤɬɭɪɧɨɝɨ ɷɤɫɩɟɪɢɦɟɧɬɚ ɢ ɇ.ɂ. Ⱥɥɮɟɪɨɜɨɣ ɡɚ ɫɧɹɬɢɟ ɂɄ ɫɩɟɤɬɪɨɜ ɤɨɦɩɥɟɤɫɨɜ.
ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ
1. ɏɪɚɧɟɧɤɨ ɋ.ɉ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɟɥɹɟɜ Ⱥ.ȼ. // ɀɭɪɧ. ɫɬɪɭɤɬɭɪ. ɯɢɦɢɢ. – 2002. – 43, ʋ 1. –
ɋ. 151 – 155.
2. ɏɪɚɧɟɧɤɨ ɋ.ɉ., Ȼɚɣɞɢɧɚ ɂ.Ⱥ., Ƚɪɨɦɢɥɨɜ ɋ.Ⱥ., Ȼɟɥɹɟɜ Ⱥ.ȼ. // Ɍɚɦ ɠɟ. – 2005. – 46, ʋ 4. – ɋ. 741 – 746.
3. Sheldrick G.M. // SHELXS-97 and SHELXL. Program for refinement of Crystal Structure. – Germany:
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4. ɇɚɤɚɦɨɬɨ Ʉ. ɂɄ ɫɩɟɤɬɪɵ ɧɟɨɪɝɚɧɢɱɟɫɤɢɯ ɢ ɤɨɨɪɞɢɧɚɰɢɨɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ. – Ɇ.: Ɇɢɪ, 1966. – 411 ɫ.
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