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(II)
02.00.04 ­



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.. . : - , , , .. : . ..

:

:

5 2013 15.00 446 501.001.90 .. (119991, , -1, , .1, . 3, ). .. : . , , . 27. : vak.ed.gov.ru « 1 » 2013 .

501.001.90

..


(II) - Cu-C(sp3), (II) ­ . , , [CuIIL(tptm)]n+, L = F, Cl, I, Br, CH3CN, tptm = -C(S-C5H4N)3, n = 0;1. , . (I) (CH3, CR1R2OH CH2CR1R2OH .), - , Cu(II). , , . , , , C-Cl .. , , 10-2 - 10-6 , 77 , , , , . , , (I) , (I) . , , (II) , - Cu(II)-C . , , (R4N+)2[CuCl42-], . (R4N+)2[CuCl42-] , , . , , , (II), . : , ,
3


, . : - 77-120 . Cu-C, . . .





, (II) (NR4)2CuCl4. , , (CuCl2R` CuCl3R`- ). , CuCl2R` CuCl3R`- - Cu(II)-C(sp3). 0.3-0.5, +0.8 - +0.9. - , Cu-C CuCl2R` 20 /, Cu-C Cu- . (II) , -, . 50 , , - . (II) , , , ,
4

. C-Cl,


CCl4, . 95% . , . (II), . AIS «Atmosphere, Ionosphere, Safety» (, 2010, 2012), 15- « » (, 2012), « » (, 2010), 6- 7- - « » ChemInt ( , 2011, 2012), 27- 30- - ( , 2009, 2012), 23- « » (, 2011), «» (, 2010, 2011). . , , , - , , . 118 , 36 28 . 158 . , (II). , , . . (II). , .
5


, , , , , (II) . , , Cl-Cu2+, , 1-Cu 2-Cu. 1-Cu , , 2-Cu, g-. (NR4)2CuCl4 , R' = (C6H12)N+(C6H13)3 Cu(I)Cl32-, R' Cu(II)Cl3R'-. , , . (II), , , - -. B(38HF)P86, (II) . ( (II), , ), (2-, ) () . (II) 2- . -175 (N(C8H17)3C7H7)2CuCl4 10-3 . (NR4)2CuCl4 2- 77 , = 405 . 77 120 . HP 8453. - "Varian-E3" 77 .
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, . .. ( ..). - . - . , - ( -). CuCl42- Gaussian 03 (DFT) PBE/6-311G++(3df,3pd) , , PBE /6-31G++(d,p) , . . - ORCA DFT/B(38HF)P86 (PPP) , IGLO-III IGLO-II . - PBE0 def2-SVP. CuCl42- N(CH3)4+ ORCA DFT/B(38HF)P86/def2-TZVPP RIJCOSX. TD-DFT/B(38HF)P86 aug-def2-TZVPP , , def2-TZVP . COSMO 2- . 0.91. Cu-C , . DFT/B(38HF)P86 aug-def2-TZVPP , aug-def2-TZVP , , def2-TZVP def2SVP ORCA.
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, ( NBO) DFT/PBE/6-31G++(d,p). , : (NR4+)2CuCl42-* (NR4+)(R`)CuCl32- + HCl (NR4+)(R`)CuCl32- (NR4+)[CuCl3R`] (NR4+)[CuCl3R`-]: (NR4+)[CuCl3R`-] [CuCl2R`] + (NR4+)Cl
-

, , , 1-Cu, [CuCl2R`], 2-Cu - [CuCl3R`-]. . - (NR4)2CuCl4 2- 77 22515 -1, 24380 -1, 29145 -1, 33810 -1 41260 -1 (. 1), . 2- 77 405 CuCl42- (. 2). 22000 -1, , 37700 -1. 15000-26000 -1 : CuCl42- 22515 -1 24380 -1, , 18860 -1, 23695 -1 22065 -1. 108 22000 -1 , 1000 -1 (. 3). 15000-20000 -1 , 19000 -1.

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. 1. - ((N(C6H13)4)2[CuCl4]) 2- 77 () ( ).

. 2. - (N(C6H13)4)2[CuCl4] 2- 77 . , .: 0 (), 6 (), 12 (), 22 (), 38 (), 60 () 90 ().

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. 3. - (N(C6H13)4)2[CuCl4] 2- = 77 K (), 95 K (), 100 K (), 103 K (), 105 K ().

18860 -1 23695 -1 , (. 4), 22065 -1 .

. 4. ) (N(C6H13)4)2[CuCl4] 18860 -1 23695 -1 () 22065 -1 () ; ) 1-Cu 2-Cu (Lobanov et al.).

(NR4)2CuCl4: , CuCl2R` (1-Cu), 100-110 , , CuCl3R`- (2-Cu) 100 K (. 4). , ,
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18860 -1 23695 -1, CuCl2R`, 22065 -1 CuCl3R`-, - . , 37700 -1. , (I) - Cu(I)Cl32- ( (NR4)2(CuCl4)) Cu(I)Cl2- ( Cu(I)Cl32-), , , . 37700 -1 , -, Cu(I)Cl32-. (NR4)2(CuCl4) 29145 -1, 33810 -1 41260 -1 . , , - . - CuCl42- + 2(N(CH3)4 )2CuCl4 (. 5), . 5. (N(CH3)4+)2CuCl42-, DFT B(38HF)P86/def2(II) TZVPP/COSMO. . . 1 2CuCl4 . B(38HF)P86 . B(38HF)P86/aug-def2-TZVPP/COSMO CuCl42- . 0.91 1000 -1 (. 2).

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. 1. CuCl42-, DFT

PBE/6-311G++ (3df,3dp) * B(38HF)P86/def2-TZVPP/COSMO** (EXAFS, Golubeva et. al.) (XRD, Clay et. al.)
* CuCl42-. ** (N(CH3)4+)2CuCl42-, . 5.

R Cu-Cl, A 2.322-2.327 2.266-2.272 2.25 2.230

133.9-134.2 130.7 129.9

. 2. (N(CH3)4+)2CuCl42- (. . 5)

, 22515 24380 29145 33810 41260

1

B(38HF)P86/aug-def2-TZVPP/COSMO , -1* 23934 0.0002 25030 0.0168 25143 0.0166 29105 0.0042 33183 0.0078 33356 0.0378 33952 0.0417 33863 0.0133 40994 0.0618

*

(N(CH3)4+)2CuCl42- - , , B(38HF)P86/aug-def2TZVPP/COSMO, (. 6). B(38HF)P86 g- CuCl42- (. 7), .

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. 6. - c 2- 77 ( ) (N(CH3)4+)2CuCl42(B(38HF)P86/aug-def2-TZVPP/COSMO) ( ).

. 7. g- CuCl42-, .

, , . 8 , , , , , (. 9). , Cu-C 17 240 /. , , , (. 10).
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. 8. Cu(II) 1-n CuClnCmH2m+1 , n = 1, 2 3, m = 1 3.

. 9. [CuClCH(CH3)CH2N(CH3)3]+ (ClC3), [CuCl2CH(CH3)CH2N(CH3)3] (Cl2C3), [CuClCH(CH3)C3H6N(CH3)3]+ (ClC5) [CuCl2CH(CH3)C3H6N(CH3)3] (Cl2C5).

)

)

. 10. ) [CuCl2CH(CH3)C4H6N(CH3)3]ClN(CH3)4+, (Cl2C6+Cl-+NMe4+) ) [CuCl3CH(CH3)C4H6N(CH3)3]-N(CH3)4+, (Cl3C6+NMe4+).

, . 3. , CuCl2R` , g- . 3. , g- , . , , g-, , g- , , .
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CuCl2R` g R4N+.
. 3. g- , B(38HF)P86

g [CuCl2C3H7]Cl2C3 Cl2C4 ClC5 Cl2C5 Cl2C6 Cl3C6+NMe
4 +

1

g

2

g

3

2.023 2.029 2.027 2.004 2.021 2.018 2.005 2.024

2.032 2.037 2.035 2.027 2.029 2.027 2.084 2.033

2.098 2.122 2.113 2.044 2.088 2.080 2.112 2.082



C , CuCl3R`-, , , . 2- (.11) , CuCl2R`, . - CuCl3R`- g- () , - Cl3C6+NMe4+ (g1 = 2.005, g2 = 2.084, g3 = 2.112, (Cu)1 = 22.1, (Cu)2 =6.9 , (Cu)3 = 3.9 ). .12 , . , , , CuCl3R`-. , CuCl2R`. , , , , -.

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. 11. (N(C6H13)4)2[CuCl4] 2- 77 ( ) ( ).

. 12. CuCl3R`-, (N(C6H13)4)2[CuCl4] 2- 77 ( ) Cl3C6+NMe4+ ( ).

- CH3CH()(CH2)3CH3 CH3CH2CH()(CH2)2CH3. - . CuCl2R` . (NR4)2CuCl4 . 11. , . - CuCl3R`-, , - (g1 = 2.005, g2 = 2.084, g3 = 2.112, (Cu)1 = 22 , (Cu)2 =8 , (Cu)3 = 7 , . 12).
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, , (N(C6H13)4)2[CuCl4] CuCl2R` CuCl3R`-, R` - (-C6H12)N(C6H13)3+, (. 10). , , , . CuCl3R`-, , . , CuCl2R` CuCl3R`-, . (. 13) , . - , CuCl2R` 35765 -1 37070 -1, CuCl3R`- 36050 -1. (N(C6H13)4)2[CuCl4] - CuCl42-, CuCl2R`, CuCl3R`-, CuCl32-(. 4, . 14).

. 13. c Cl3C6+NMe4+ ( ) Cl2C6+Cl-+NMe4+ ( ) , B(38HF)P86/aug-def2-TZVPP/COSMO CuCl2R` () CuCl3R`- ().

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. 4. (N(C6H13)4)2[CuCl4] 2- 77

, 18860 23695 35250 2 3 2 2 2 3 4 3 4 4 4 206 772 251 438 914 381 126 773 147 413 899 5 0 5 0 5 0 0 5 0 0 0

-1

CuCl2R`*

CuCl3R`-*

CuCl42-**

, -1 ( ) 18865 (0.0220) 18985 (0.0010) 23645 (0.0791) 35765 (0.0218) 37070 (0.0179) 22010 (0.1006) 36050 (0.0110) 22515 24380 29145 33810 41260 36230 39600 43480

CuCl ***

23

* - ** . *** (Stevenson et. al.)

. 14. - c 2- 77 90 (), ( ), CuCl42- (), CuCl2R (), CuCl3R(), CuCl32- ().

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- , 30% CuCl2R' (. 15). CuCl3R'- Cu, , CuCl2R' . CuCl2R'. Cu CuCl2R' CuCl3R'- 0.25-0.45 a.u. , (I) (. 5), .. . (II). : g ge, .
. 5. Cl2C6+Cl-+NMe4+ (CuCl2R') Cl3C6+NMe4+ (CuCl3R' )
-

Cu Cl2C6+Cl-+NMe4 Cu(I)Cl2
+ +

(NPA) R 0.67 0.67 Cl -0.74 -0.68 -0.79 -0.89

Cu R Cl 0.36 0.44 0.50 0.45 0.07 0.05 0.01

0.81 0.36

Cl3C6+NMe Cu(I)Cl3
2-

4

0.91 0.67

, Cu * (NBO)

. 15. Cl2C6+Cl-+NMe4 ( ).

+

Cl3C6+NMe4

+

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CuCl2R` CuCl3R`- - Cu-C(sp3) (. 16). 4s 4- , - 3d- .

. 16. Cu-C Cl2C6+Cl-+NMe4+ Cl3C6+NMe4+ ( ).

(II) -2 10 -10-6 . : Cu-C, . , Cu(I) , . . 17 - CuCl2R` Cu-C. Cu-C (10-20 /), . , (77-120 ) (II) . , - , CuCl2CH3 (CH3) (II) (.18). , (II) .
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. 17. Cu-C [CuCl2CH(C2H5)C3H6N(CH3)3], [CuCl2CH(CH3)C4H8N(CH3)3] [CuCl2CH2C5H10N(CH3)3], Cu-C .

. 18. CuCl2CH3.

, - :

21


P ­

, ,

1.0

0.8

0.6

n/n0
0.4 0.2 0.0

100

120

140

160

180

T, K

. 19. (N(C8H17)3C7H7)2CuCl4 77 (), 105 () 150 ().

. 20. (N(C8H17)3C7H7)2CuCl4 () 2- () .

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(II) . , , , . , 2- 77 . , (NR4)2(CuCl4) 77 2-. 170 , (CuCl2R`, CuCl3R`-, R`) (. 19). , , 50 (. 20), , . 1. (NR4)2CuCl4 2- - , : ) (II), (CuCl2R` CuCl3R`-) - Cu(II)-C(sp3), ) (I) ) , . .

2. , Cu-C CuCl2R` 20 /, Cu-C Cu- . 3. , CuCl2R` CuCl3R`- , - , 50.

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: 1. Golubeva E.N., Gromov O.I., Zhidomirov G.M. Cu(II)-Alkyl

Chlorocomplexes: Stable Compounds or Transients? DFT Prediction of their Structure and EPR Parameters // J. Phys. Chem. A. 2011. V. 115. P. 8147-8154. 2. Gromov O.I., Zubanova E.M., Golubeva E.N., Plyusnin V.F., Zhidomirov G.M., Melnikov M.Ya. UV­Vis Identification and DFTAssisted Prediction of Structures of Cu(II)­Alkyl Chlorocomplexes // J. Phys. Chem. A. 2012. V. 116. P. 11581-11585. 3. Gromov O.I., Golubeva E.N., Zhidomirov G.M. Structure of Cu(II) Alkyl Chlorocomplexes formed via tetrachlorocuprates photolysis: EPR, UV-Vis and DFT study// Book of Abstracts of AIS-2012 "Atmosphere, Ionosphere, Safety" Kaliningrad, June 24-30 2012. P. 119-120 4. Gromov O.I., Zubanova E.M., Golubeva E.N., Zhidomirov G.M. Structure of Cu(II) Alkyl Chlorocomplexes formed via tetrachlorocuprates photolysis: EPR, UV-Vis and DFT study// Proceedings of XV International Youth Scientific School "Actual problems of magnetic resonance and its application", Kazan, 22-26 October 2012. P. 173-176. 5. .., .., .., .., .. (II) ­ // XXX - , "", , 2012. C. 12. 6. .., .., .., .., .., .. UV-Vis Cu(II) // VII - " " ChemInt2012, , 15-17 2012. C. 19.
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7.

..









2011», . 2011.



//

«8. .., .., .. CuCl2...CH(CH3)2// VI - " " ChemInt2011, , 10-13 2011. C. 18. 9. .., .., .. - 2011. 10. .. - Cu(II)-C(sp3)// « -2010», . 2010. 11.Gromov O.I., Golubeva E.N., Zhidomirov G.M. Complexes with Cu-C(sp3) Bond: the Quantum-Chemical Study// Book of Abstracts of AIS-2010 "Atmosphere, Ionosphere, Safety" Kaliningrad, June 21-27 2010. P. 199-201. 12. .., .., .. (II): // " ", , 6-10 2010. C. 60. 13. .., .., .., .. // XXVII , // XXIII « », , 23 ­ 4

,

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. , 2009. C. 13.

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