Fe (III), Co (II), Ni(II), Cu(II) -3,3'-(5- -1,2,4- Co(II), Ni(II) 121
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- Theodore Thomas Hart
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1 .. -1,2,
2 .,. -1,2,4- / -. : ,, - -1,2,4-. (5-, - (), - -3,3-(5--1,2,4- - :, -..,, -,, -. :.. ; -. ; - - ().., 2002.,.,
3 ,2,4-, 5--1()-1,2,3, ,2, ()-1,2,3, ,3'-(5--1,2, , - 5-, 3,5-- 1,2,4-5--1()-1,2,3, ,2,4-, 1- )-5- -1,1 -(4--1,2, ,2,4-1- 1, ,2,4-1- 1, ,
4 ,2, ,2, ,2, ,1'-(4- -1,2, ,1 -(4--1,2, ,1 -(4--1,2, ()-1,2,3, ()-1,2,3,4-- 1, ()-1,2,3,4-1,3-1, ()-1,2,3,4-1,3-1, ,2,4-.,, ,2,
5 ,2, , ,3 -(5--1,2,4-) Fe (III), Co (II), Ni(II), Cu(II) -3,3'-(5--1,2, Fe (III) ,3 -(5- Co(II), Ni(II) u(ii) ,2, ()-1,2,3, , 1,2,4-5--1()-1,2,3, ,2, ()- 1,2,3, "
6 -» ,3 -(5- -1,2, » ,2, ,2,4-1,2,3, ,2, , ) ) (4--1,2,4-) (I-IV) ( ,2, (V-VII) ,2--(1,2,4--1- (1) (1,2,4--1- (X, XI) (5- (XII-XVII) 199 8
7 ,3--(5--1-)-2-- (XXI), 1-(5--1-)-3-(5--2-)- 2- (II) (II) Ni (II) Cu (II) ()- 1,2,3, ,2,4-5--1()-1,2,3, " "
8 , MNDO, AM1, PM ,2, ,3-(5--1,2, ,2,4-3,5--1,2,4- (5-4--1,2,4-1,2-1,2-5- 3,4,5--1,2,4-
9 1,5 1,5--1,2,3,4-1,2, ,2,4- «- 11
10 ,,, - -1,2,4- () 5--1()-1,2,3,4- (5-).,,, -,. -, - ). -1,2,4-5-, ,, ;,
11 , - 1,2,4-.,,.,. -, -,, , - -., -, - -, - -1,2,4-, - -,. -,. :. ),. - :,, ; ; 13
12 4--1,2,4- - ; ; ; -. -,, - -,. :, 5- N,N- ) ; ,2,4-1- 1,2- - ; -1,1'-(4- -1,2,4--3,3'-(5--1,2,4-- (), (1,2,4--1-; 1,2,4- -, ; - ; - -, 1,2--., - - : 14
13 , (. ) (. )., , (. -.) - (). - - () (5-), -,, - (1992.).,, -, - -1,2,4-,
14 1. -1,2,4-, 5--1()-1,2,3,4- -, ,2,4- - -,,,,, [1], [2] ,2,4- [3]-[5], - [6]-[8] [9]-[15]. 16
15 - - 5-, 5--1,2,4- (5- ) 3,5--1,2,4- (3,5-) -1,2, [16], [17]. - 3, ,2,4- (I) [18], (II) (III) [19], [20]. HN NH N NH N NH 2 HN N H N N N H 2 N HN Ph N N Ph H H I II III 3,5--1,2,4-- [21], 2()-, 4(H) , - (IV-VI), (VII, VIII) [17]. [16]. H 2 N N NH 2 H 2 N N NH Ph HN N N N IV V N NH2 N NH2 NH NH2 N NH NH NH HN N N NH N N HN NH N NH 17
16 VI VII VIII IX X H 2 N N N H HN N N H H N N H XI - 5- (V) [21]-[23]. 3,4,5--1,2,4-, [24] ()-1,2,3,4-1951, 5- (XIII), (XIV), - [25]., 1-R-5-, -,, (XV). (XVI) [26],, -, (XIV)., (XV) (R=) (XVI) (R=CH 3 ) [27]. H N N H XII HN N N N N N HN N R N N N H2N R HN N N R R XIII XIV XV, 5-,, [27], [28], [29]. 18
17 R N N N N + R H-N N N N HN N N - RN N N H 2 N R R H XVI XVII XVIII XIX HN N N N NH 5-. [27], 5-,. 5-- [30]. [31] 5-., 5-, -., () - 5- ( ), [6]-[8] ) =6.69.,, (6.5.) [32] ,,, ( ) :,. =6.57. ( 1 ),, 19
18 .,, , -, (CCl 4,, ), , , - NH - NH,. [33], -, 5- ( NH ; NH ) : , NH [34], , - NH,, , , ,,, -, C=N =N,, I, -., - [35] , [33] [36], N=N C=N [36]
19 ,. 1.,, 5-,, [30]. (l 4,,,, ),., , , [26]. - [22] [19] [27]., [28], [29] 5- (.1). 5-,. 1 %
20 XXVI, XXIX, XXXII ,3 -(5--1,2,4- (XXVI) 22
21 ,3 -(5--1,2,4- (XXI) 23
22 ,3 -(5--1,2,4- (XXII) ,3'-(5--1,2,4- -3,3'-(5--1,2,4- () - [37]., -3,3'-(5- -1,2,4-. (- ) ( ) NH ( )., (), =N. -,, ,, [38] , - NH. NH , ,, [8]. 24
23 - N (1). [39].,,, -. -(5- () [40] , , [41].,, C N NH ( ) ,, CH ( )., -.,, -. 1, - [40]. 1-3). [7]- [9] , [9]-[15]., - - [7]-[9] [42],. 25
24 -,,, , 1--, 2--5-, - [39]. MNDO, AM1, PM3. MNDO MINDO/3,. - MNDO -. -, -.. 2, MNDO, AM1, PM3. - -, MNDO (H)- 2-(H)- 1-(H)-., () 2. 26
25 MNDO AM1 PM () () ()- 2-() ,5-- 2, , ()- 2-() , (ab initio) [43],, 2-(H)-. 1,2,4-- [44] - MINDO/2 CNDO/
26 - 1-(H) 4-(H) 1,2,4-1-(H).,, 1,2,4-, [45],,. 1,2,4-, - N-N Å-, -, MINDO/2 ( Å- ). N-N 0.01 Å Å., -. C, : - (, -, )?, [46], - - (, ), -., [46], - MNDO ,2,4-, - MNDO ( 1). 28 3
27 5-1,2,4- () MNDO AM1 R(5) H(4) H(1) H(2) H(4) H(1) H(2) H NH 2 CH ( )* ( ) ( ) Cl ( ) C=N ( ) NO ( ) ,2,4-, MNDO,,,, 1-()- -., MNDO 1,2, , 5-, 3,5--1,2,4-5--1()-1,2,3,4-29
28 1,2,4-, [46], - 1 ab initio 3- -1,2,4--5-1,2, [46] 1-()- 4-()- 1,2,4-4-()-, ab initio 1-()-. - 1,2,4- MNDO, 1, 3 (sp 2, - - ). () -,, -, 5--1,2,4-,. -. 3,5--1,2,4-, -., 5--1,2, ,2,4-, ()-1,2,3,4--1,1 -(4--1,2,4-,, sp , [29], [45]. 30
29 H N H N C N H C N 4 2 H 5 H N H H N C N C N 8 7 Å, () 5--2-()-1,2,4- (MNDO, AM1, PM3) MINDO [3, 4] (6)=N(3) N(3)-C4) C(4)=N(2) N(2)-N(10) N(10)-C(6) N(7)-H(8) N(10)-H(1) (6)-N(7) LN-C(6)-N
30 LC-N(3)-C LN-C(4)-N LC-N(2)-N LN-N(10)-C LH-N(7)-H (Å), () 5--1()-1,2,3,4- MINDO [3, 4] (2)-N(5) N(5)=N(8) N(8)=N(7) N(7)-N(6) N(6)=C(2) N(1)-H(4) N(5)-H(9) C(2)-N(1) LN-C(2)-N LC-N(5)-N LN-N(6)-N LN-N(7)-N LN-N(6)-C
31 LH-N(1)-H , 4, 5, - C N, C=N N=N.,, 5- C(6)=N(3), N(10)-C(6), C(4)=N(2) , 5- C(4)=N(2), C(2)-N(5) N(7)-N(6) 5-, , -, N C = 1.37 Å ( H 2 C=NH Å). - : -,, -,,..,., 5--1,2,4-3,5--1,2,4-, - [44], [45],, sp 2 - sp 3 -., sp 2 sp C C, -,, -.,. - NH 3 ( 4.2 ). 33
32 , ( ), (5-6 ). [6], -,, () -, -,,, -., -, - [48]. MNDO 5--1,2,4-, 5-, 3,5--1,2,4-4--1,2, t= º., 5--,, C H. - : - C N N H, - NH 2 C N, - - N H, > N H , , - H 2 N C N, -. -,, - 5-,,,. MNDO
33 ( Å, ) 5--1,2,4- ( MNDO) (6)=N(3) (3)-(4) (4)=N(2) N(2)-(10 ) N(7)-H(6) N(7)-H(8) N(10)-H(1) C(6)-N(7) LN-C(6)-N LC-N(3)-N LN-C(4)-N LC-N(2)-N LN-N(10)-C LH-N(7)-H LH-N-C=N 29 LH-N-C-N sp 3 -, (, - 35
34 )., ) , sp 2 -.,, C N., ,2,4- (4-) [48], [49]., [48] ab initio.,, -. [49], N 4- INDO. N N N N N N N N N N N N N N H H H H H H H H - -1,1 -(4--1,2,4-, - [50], [51]. MNDO, - [47], [52].,,. (I IV),, - 4- () ,2,4- () (.7). 4- -, 5 3. (I IV). N N 36
35 N N N + Br(C 2 ) n Br k 1 N + N N 2 ) n Br Br 2 NH 2 N + N N (C 2 ) n Br Br + N N N k 2 N + N N 2 ) n N + N N Br NH 2 Br(C 2 ) n Br + H 2 O n = 1, 2, 3, 4. 2 NH 2 (I IV) k 0 Br +, NH
36
37 , (I IV) 3, 5, 3, 5. -., -. : 1, 2, 3, 4, 5 6 3, 5, 3, 5, -., (. 8) (+0.132,+0.170). 8, (Q) Ia IIa IIIa IVa (+0.060,+0.105), (+0.103,+0.340), (I) 2 4,, sp 3.,,,,, -.,, -, - 101
38 5 5, 1 (- D D 2 O). (I-IV) ,2,4- (). -.,,. -,, Br, 5. Br. 5 Br 1.92 Å,.. 4 () ,2, ,2,4-4-,. (I) 5 N 1 5 N 4 -,
39 . 5. (Å) () (4--1,2,4--1- N 4 N 6, ( N N )., MNDO, AM MNDO (4--1,2,4--,. 103
40 2., - -1,2,4-5--1()-1,2,3, , ,2,4-1- 1,2- - 1,2, S N ,, [53]-[57]. S N 2, l = 3 + l,, [36].. 6. l - + l = + 1,, [36]. 104
41 , 20. -, -,, -., -. -, [58] -. 4-, -, -., 4-- -, 1,2,4-. 4-, , ,2, ,2-, -,
42 , -, % (100 ) ,2, ( 1 ), t - (). 4-1 ): 1-0,52,2-0,54,3-0, ( 1 ): 1-0,49,2-0,78, 3-1,
43 4--1,2, t, t, t, =0.52, =0.49 =0.54, =0.78 =0.49, =
44 , cp , ,2, E. S / ) LgA / ) / ) /( ) , -,
45 -, -., : 2-4:1, -,., - : : (4:1) ,2,4-: (4:1) t, t, =0.58,.58, =0.56. =
46 =0.53, =0.81. =0.49, =1.02. t, t ; : 4-60 %, % ,2-., - 4-1,2- - (), (), - (). 110
47 - -, : n , : k1 A B C, k2 A B D. 111
48 k 1 k 2 - : 2 1 X 2 b e d ln x dt i i t t i 1 K b 1 i b e, 1 i ( a 2 b) 1,, b (.), (.), t i i 0 x dt i d 0 ln x 1 i c. dt tt i, - - i Ô i, -., - Ô i, : k1 2A B P, k2 2A B C. 1 1 k 1 : k 2 112
49 113 = 2 (x + y)/c 0 A,, ,2-, i = a t b i, b. x i = t b i, -,, - :, ln, / 1 1 ln t t t A A A t A A t dt dt dt C K C t C K dt C K K C t K, b C A t dt t a A dt x i i t b i t i i i i, b t a b A t C dt a i i i i t i i i, ln 0 i i i t t i t x C b dt x dx dt X d i b b a b b a t dt a dt i i t t i i i i
50 4., : k1, k2 D E,, - k 1 : k 2 = 2,3,4,, - - k 1 / k 2. k 1 t : 114 B K 1 k t 1 2 k 1 d 1 1/ 1 2, k 1 k ; k = k 2 / k 1 ; b = [] / [ ]. k 1 / k 2 2 0, t. - IBM-PC-486 DX , - -, -, - -. ), y (x) Q Q n i0 2 yx f. i x i, -
51 ., - 4-1,2- (), (), ()., - 0 t k 1 k 2 I t F t 0 xdt fk k. 1, 2 : -, - I t - k 1 k 2 k 1 k 2, i (.) C i (.) (1,2), (3), (4) -, , (=0.56, =0.27. (K 1 =0.039, 2 =0.028 )
52 K 1 K ,2,4-, -. - K 1 K 2 5-6, ,2,4-1, (. 13,14) ,2,4-1,2- \ , / ) / ) ± ± ± ± ± ± ± ± ,2,4-1,2- (), =70 =80 =90 =100, ± ± 0.83± 1.81± 1.50± 2.96± 2.72±
53 4--1,2,4-1, Ea, LgA , S, /() , ,2,4-1- 1,2--, S N 2-, 1-1,2-:, -,,, -, ;,, - S N 2- [57],, 4-1, , - ; - 4-1,2-, 4--,, -,. 117
54 [59] - N,N- 1,2-, ,2- [59],., - 1,2-- ()=45-70, (/()=(-130) - (-200), -. 1,2-,, - S N [59]. S N 2-, - 1, ,2-, 1,2- -, , ,2-25 [35] % ) % ). ). ) ±2 35±4 0.30± ±0.30 [55] -, 118
55 - (, ) -. : -,, , -,, 1,2- ().. 9 -, ,2- - 1,2- (. 10) ,2- - H = H =-52.0 (MNDO) H =-14.6 H =-10.2 () - 1,2-,, 119
56 , - 3-, 4- (. 11): ,2-4--1,2,4- R-CH 2 -CH 2 -X S N 2-,. 16,. 16 R-CH 2 -CH 2 -X S N 2- ( =1 3 2 ) 6 5 S, 25 R-CH 2 -CH 2 -X F ,2,4-1,
57 , - 1,2-4- N,N- [59],, [55] -, S N 2- -,,, -. -, - - s , -. -,,, S N "", -. - S N S N 1 S N 2,,.,, :, -., 121
58 ,,. - -,, 1, ,2,4-,, - (5.60) ,2,4- () 4--1,2,4-,, ,., -, -,,, -. 1,2- -, 5- () s 3., * ) s 3.
59 - 4-1,2- - s 3 -, ,2- - [60] ,2,4-,, -,. -,,., () 1,2- ) 4--1,2,4-.,.,., -, -, -,., 1,2,4-, -,,, ,2,4-, -, , - 1,2,4-5-- [1], [61]-[68]. 123
60 NH 3-3(5) - - [69] (. 13) ,2, ,2,4- [69] 5-5-AT - [66]. N(2) N(4) [70], [71]. - (5.1 ), (236.3 ), - ( ) ( ) [72] ( ) [67]. -1,2,
61 -.,, %. - 0, / - -, ,2, [73] [61] [73] [78] [79]; 159 [61,72] [80] 50 (20 ) [77]. 23 (23 0 ) [73]. [80].., - -.,.,...,., -.,.,.,. (75 0 )-.,..,.,.,.,. [66] 109 [75] [76] [1] [61] 77 [79] 77 [79] 11.08; [76] 5.93 [66] 6.03 [67] 2.27;2.1 9 [76] [61] 2.55 [62] 2.98 [59] 3.23 [58] 4.04; 4.17 [76] 4.17 [61] 4.50 [77] 1.82 [66].-,. -,. -,. -,. -,. -, ,2,4-,, sp 2 (). - - S N 2 ( ).,, [53]., - 125
62 (Y +...R..X - ),,, [53]. -, - [66]. 4-3,5-, N- N(1)-, 1,4-2,4- [61], [64]. R 1, R 2 : H, Alk, Ph, Ar;R 3 : Alk;X:Hal, CIO 4-,. (, ) [81]-[83], - [84]-[86] , , -, - - [82], [83] ,2, ,.,, [1] [81],, -
63 4-- 1,2,4-1,3-1,4-,, ,2,4-: N(1) N(4) - N(1)-, [64], [65], [87]. 4- N(1)- 1,2,4- [83], [85], [86], [88], [89]. 4--3,5-R-1,2,4-- 1,2- - [85] 1-- 1,2, %. 4-, ,., ,1 -(4--1,2,4- [51]. = 1 (I), 2 (II), 3 (III), 4 (IV). -, -, [81] ,1'-(4--1,2,4-- ) (I-IV),,, - 127
64 ., ,, 1-1,1 -(4--1,2,4- (I-IV) -, %.,,, -1 1,, ,3250, 1650 (NH 2 ), 1515,1500,1460,1440, 1400,1320,12600,1100, 1080, 1035 (), 667, 658 () 5.04 (2 2 ),7.31. (4, NH 2 ), 9.28 (2, ), (2) II , 3250, 1655, 1645 (NH 2 ), 1580, 1545, 1490, 1450, 1410,1330,1230, 1085, 1035 (), 638, 630, 623 () III , 3255, 1665, 1650 (NH 2 ), 1590, 1550, 1495, 1440, 1415, 1305, 1260, 1230,1092,1080,995 ), 632, 624, 611 ) 4.98 (4, 2 ), (4, NH 2 ), (2) 2.50 (2, 2 ), 4.50 (4, CH 2 ),7.06 y.c. (4H,NH 2 ), 9.23 (2, ), (2, ) IV , 3300, 1635 (NH 2 ), 1580, 1545, 1495, 1470, 1440, 1300, (4 2 ),4.40 (4, 2 ), (4, NH 2 ), 9.2
65 1275, 1250, 1078, 1028 ), 630, 625 () (2), (2, ), %,% N N I II III IV C 5 H 10 N 8 Br N C 7 H 14 N 8 Br C 8 H 16 N 8 Br ,1 -(4--1,2,4-(I) 129
66 ,3-(4--1,2,4- (III) ,4-(4--1,2,4- (IV) ,3-(4--1,2,4- (III) 130
67 ,4-(4--1,2,4- (IV) ,2-(5--1-) (II) (5--1-)-2- (5--2-) (III) 131
68 ,2-(5--2-) (IV) (II-IV) 5-1,2-132
69 (II-IV) 5-1, (XV-XVII) - 5-1,3-133
70 (XVIII-XX) - 5-1,4- (I-IV) , [90]-[92]. - [91], [92] , [69], [90] [75] [91], [92], [94], [95].,, [7], [91], [96], [97], [98]. 1,2,4-, - -. [96],, -,, -,,.,. [91], [92], [96], [98], [99] (I-IV) , , , -, - (). 134
71 [96] [92]. (I-IV) [96], [100] ,, [96], (- ) (I-IV) -d 6 N-CH ,, [101] ( ) [102] ( CDC1 3 ). NH 2 -rpyn ( ) - (I-IV) 4--1,2,4- ( ) [81],. - NH 2, ( +1 + ). [103] 1, ,2, (3) (5) ( ) [61]. 1 (I-IV) ,, D 2 O D, , (4--1,2,4- (I) [3], - 135
72 [61] -. - (. 26) ,2, ,2,4- - (5) (5'),. - (3) (3'). -, (5) (3) ,1 -(4--1,2,4-, 1,2,4-,. -3,3' -(5--1,2,4- (III), - (II), (II) (II) [104]. (II) 5,5'--3,3'-(5--1,2,4- [3]. II (3:1). -
73 . 0,48 0,16 0, Enfar-Nonius CAD-4 (, -, 0/20-, 20=50 ). -, : 3 3 2, 5 6 3, 6 8 4, )=19, : a=8,216(2), b=18,510(4), c=8,389(2) Å; =106,28(1), V=1224,6(5) Å 3, Z=4, d.=1,931 3,. 2 1 /n. - - SHELX R () 1209 F(hkl) I>2 (I) ( 157 ) II -. (N 4 C 2 H 4 ) 2 (CH 2 ) 2 2+, -, Br., - N(1)-(1), (1)-(1 ), (1 )-N(1 ), N(1)- (1)-(1 ) (1)-(1 )-N(1 ) 113,5(8) 111,7(8), - (.27). 137
74 . 27. (N 4 C 2 H 4 ) 2 (CH 2 ) 2 2+, 0,04 Å N(4) 0,01 Å N(4 ). N ,7. (1)-(1 ) -, N(1)-(1) N(1 )- (1 ). N(4)-N(3) N(4 )-N(3 ) N-N (1,47 Å). N-C N-N - 1,30(1) 1,39(1) Å. 103,5(8)-111,7(8), N(4) N(4 ),, 107,7(8) 106,5(8) (.20). - -N,, N(1)-N(2) N(1 )-N(2 ) (1,33(1) 1,39(1) ). -, N-C N-N 4--1,2,4-107, (N 4 C 2 H 4 ) 2 (CH 2 ) 2 2+,. 28, (001). 138
75 . 28. II (001) - n /2. -. (010) - (N 4 C 2 H 4 ) 2 (CH 2 ) ), Br(1) Br(2) : Br(1)- N(4) 3,289(7); Br(1)-N(3) 3,405(9); Br(2)-N(3) 3,407(9); Br(2)- N(3 ) 3,408(9) Å. -,. 139
76 . 29. Br - ( (010) II -1,2,4-- -1,2,4--., ,2,4-, I-IV. 19 ( 10 4 ) , U =1/3(U 11 + U 22 + U 33 )) (N 4 C 2 H 4 ) 2 (CH 2 ) 2 Br y z U Br(1) 47(1) 1734(1) 9045(1) 47(1) Br(2) 8240(1) 5047(1) 2085(1) 48(1) N(1) 6011(9) 3789(4) 8870(9) 31(2) N(2) 7406(10) 3344(5) 8993(10) 44(2) N(4) 7274(10) 4230(4) 7199(9) 32(2) N(3) 7596(13) 4652(5) 5919(11) 49(2) C(5) 5959(13) 4306(5) 7794(12) 36(2) C(3) 8151(13) 3636(6) 7925(13) 47(3) N(1 ) 4445(10) 2365(4) 8786(9) 36(2) N(2 ) 5126(11) 1909(5) 10023(9) 41(2) N(4 ) 5643(10) 1565(4) 7728(10) 36(2)
77 N(3 ) 6241(12) 1189(5) 6565(11) 48(2) C(5 ) 4749(12) 2168(5) 7400(12) 37(2) C(3 ) 5863(12) 1421(5) 9370(11) 37(2) C(1) 4873(12) 3615(5) 9833(11) 33(2) C(1) 3606(12) 3033(5) 9061(12) 40(2) :. 20 (N 4 C 2 H 4 ) 2 (CH 2 ) 2 Br 2 d, d, N(1)- C(5) 1,31(1) N(1 )- C(5 ) 1,31(1) N(1)- N(2) 1,39(1) N(1 )-N(2 ) 1,33(1) N(1)- C(1) 1,43(1) N(1 )- C(1 ) 1,47(1) N(2)- C(3) 1,33(1) N(2 )- C(3 ) 1, N(4)- C(5) 1,32(1) N(4 )- C(5 ) 1,32(1) N(4)- C(3) 1,36(1) N(4 )- C(3 ) 1,36(1) N(4)- N(3) 1,41(1) N(4 )- N(3 ) 1,40(1) C(1)- C(1 ) 1,51(1) 3636(6) 7925(13),, C(5)- N(1)- N(2) 110,6(8) C(5 )- N(1 )-N(2 ) 111,8(8) C(5)- N(1)-(1) 130,8(8) C(5 )- N(1 )- C(1 ) 126,3(9) N(2)- N(1)- C(1) 118.5(7) N(2 )- N(1 )- C(1 ) 121,7(7) 141
78 C(3)- N(2)- N(1) 103,5(8) C(3 )- N(2 )- N(1 ) 104,9(7) C(5)- N(4)- C(3) 107,7(8) C(5 )- N(4 )- C(3 ) 106,5(8) C(5)- N(4)- N(3) 125,3(8) C(5 )- N(4 )- N(3 ) 124,0(8) C(3)- N(4)- N(3) 126,8(8) C(3 )- N(4 )- N(3 ) 129,5(9) N(1)- C(5)- N(4) 108,2(8) N(1 )- C(5 )- N(4 ) 106,5(9) N(2)- C(3)- N(4) 110,1(9) N(2 )- C(3 )- N(4 ) 110,3(8) N(1 )- C(1 )-C(1) 111,7(80) N(1)- C(1)- C(1 ) 113,5(8) ,1 -(4--1,2,4-) - 4-, -, [103] l-r-4--1,2, , (3), -. -1,1 -(4--1,2,4- - (I-IV),, -( ,2,4--1- (V-VII) (85-92 %). (V-VII), -. -, (. 21). 21 -( ,2,4--1- (V - VII), %.,,,
79 rnax,, /( ) V (NH 2 ), 1485, 1470, 1440, 1400, 1315, 1275, 1230 (), 1140(C=S) VI (NH 2 ), 1550, 1480, 1450, 1410, 1305, 1260 ), (OS) VII (NH 2 ), , 1495, 1470, 1430, 1310, 1270, 1250 (), 1145 (OS) 22 (1,2,4--1-(VIII-1) - - -, %..,.,. ) 1,,.. (CDC1 3 )
80 VIII [48] (2, N-CH 2 ), (2, ), (2, ) IX [21] (4, N-CH 2 ), (2, ), (2, ) X (2, 2 ), 4.31 T. (4H,N-CH 2 ), (2, ), (2, ) XI (4 2 ), 4.24 (4, N-CH 2 ), (2, ), (2, ) (83-92%) (VIII, IX), (X, XI), - 1,2,4--, [102], 110]., (1,2, (XI),, -, 92 %, - 5, - 45 % 24-48, [81]., -1,1 -(4- -1,2,4- -,. 144
81 [111]-[113] 5-. 1,1 --()-, 5-, 5- - () [112]. 1 -, 5-, - N(1), 5- - N(2). 2,, 1,2'- 2,2'-. - 1,1,.. 1,2'-, 2,2' ()- 5-2,2' - )-5- [113]. 1,1 --(- [113] 1,2' 2,2' 2:1, :1 (1,2 :2,2'). 1,1 --(- - 1:1:2 (1,1':2,2':1,2'), 5-1,2' 2,2' - 2: ,2'-. -.,. 1,1 '-, 1,2'-. 5-1,2-1-(5--1-)-2-(5--2-2,2'-(5--2-, - 1 [114]. 145
82 1,2'- 2,2' %.. 1,2'-, 2,2'- ( ). 1,2- [102]., , - 1, ) ,2' 2,2'- [115]. 5-(4-5-(3-2,2'- ; 2,2'-, 1,2' ,2'-, 2,2- [115].,,, - -,. 5--, ()-1,2,3, , - [41]. - 5,,, -,. -
83 5 - N(1)-, - - N (2)-., - - [68], [111]. - [68] N(2)- [116]. N(2) , -,,,,, 5- N(2)- [117].,,, () [118], , -,,, - 5-., -. - N(1)-. -,,, -, -. [116] : 147
84 - - 5-, -, - -, + - (), -, I I -1 -, I ( N(2)-) - N(1) - [119], [120] NH-.,,,,,, -, -,. + -, + - -, + -., -, [120], [121]., , [120]. -,. N(2)-, N(1). 148
85 ,. 5- [121], - N(1)- N(2)-, -,. - ( ). -,,, [122]-[129]. -. [123], [130], [131].,, N(1) , N(1)- [128] % N(1)- 40 % N(2)- [127], [128].,, , [127]. 5- ( 5-) - (C1-CH 2 -CO-R) % [111]., 5- [127],. (. H 2 SO 4 ), 5-, - N(2)- [117]. 5-- N(1)-, N(2)-,, N(2)- [123], ( ) - 149
86 35% N (1)- 65% N (2)- [132]., 5- N(1)-,. - (, CN-) N(2)-. N(1)-, N(2)-, N(1)-. -, [124]-[126], [100], [99], , 5-, -, : 3 N 5 *HCl* 2. -, ( 4). - ( 1), - -, AT (-5-) [116],,
87 ,, , 5-., % ,1 -- (5-, -., ,. -.,. 1,2- ), 1,2-, 1,3-1, , 1,2--,, - S N 1. - S N 2,, -., ,, +1-,. F - - <I -,, R-Hal., '- () '-, -., -,,. -. ). 151
88 Kat=K +, ( 2 5 ) 3 + ; Hal=Br -, l; R=(CH 2 ) 2 (XII-XIV), ( 2 ) 3 (XV-XVII), (CH 2 ) 4 (XVIII-XX), ( 2 ) 2 O (XXI, XXII), ( 2 4 ) 2 O (XXIII, XXIV)., 5-AT -, 1. - (XII-XX). - 5-AT 1 -, 1,1'- 1,2' ()-1,2,3,4-1,2-5- 1,2-. 1, , N-CH 2,, -, , -., -, : [130], [131]. -,,, - 152
89 . [130]: 1) ; 2), ; 3) -, ; 4) ; 5) -.,. -, -., [55], [132]:, * -,, -.,. :, -., -,,., [132], [133]., - 5-AT - 1,2- : 1,2-(5- -1,2,3,4--1- (XII), 1-(5--1,2,3,4--1- )-2-(5--1,2,3,4--2- (XIII) 1,2-( (XIV). 153
90 (5- (XII-XIV) - -., : , - (. 23)., - - 1,2'-. 23 (5- (II-XIV) - -.,, D (MNDO) R f *,, c 1 1,, II , 3410, 3330, 3280, 1650, c. (4H,N'-CH 2 ), (4, NH 2 ) XIII (NH 2 ), 1610, 1570, 1485, 1470, 1460, (2, N'-CH 2 ), (2, N 2 -CH 2 ), 154
91 1275,1175,1165, 1120,1115,1080, 1040, 1005 () XIV ,2920,1380, 1360( 2 ) (2, NH 2 ), (2, NH 2 ) (4, N 2 -CH 2 ), (4, NH 2 ) * - : (1:1). 1 : 4.51., , N-CH 2 (XII-XIV)., - N(2)- N(1)- [61], [111], [134]., - : 1,2 - N-C 2 [114],, 1,1'- 2,2'- - [133], [134]., NH 2. [61], [111], [134], N(1)-, N(2)-. 5-AT 1, :2.5:1, 1,2-1:3:1 (1,1'; 1,2'; 2,2')., -,. 10),, 1,1'--, 1,2'- - [111]- [113], [115]., - (XII-XIV) -. 1,5- -, 2,5- [135], [136]., -, MNDO - 155
92 (VIII-XIV) (. 23)., - 1,1'-, 1,2'-, 2,2'-. - R f.. 23). R f. (1:1) 2,2'- (XIV), -, R f 1,1'- (XII) ()- 1,2,3,4-1,3-1, ,3-1,4- XV-XVII VIII-,, - -, 1,2-1,1'- 2,2'-., -, 1,2-, - 1,2-: 1-(5--1-)-3-(5--2- (XVI) 1-(5--1-)-4-(5--2- (XIX), (. 24). 1 -,. [69], [3] , 1460, 1445, , (XV-XX) 1600, I, C-N N-N , , ,. 156
93 , (XV-XX) ,. 1 (XV-XX) - (N-CH 2, 2, NH 2 ), (. 24). (V-VII) (XVIII-XX) 24 =3 (XV-XVII); 4 (XVIII - XX). -, %.,, D R f,, 1 1,, XV , 3350, 1640, 835 (NH 2 ), 1595, 1575, 1540, 1525, 2.22 (2 2 ),4.13. (4, N 1 -CH 2 ), (4H,NH 2 ) XVI , 1415, 1290, (2, 2 ), ,1085,1015,. (2H,N'-CH 2 ), , 1055, 1030 (2H, N 2 -CH 2 ), ),. (2, NH 2 ),
94 . (2, NH 2 ) XVII XVII XIX XX ,2870,1380, 1350 ( 2 ) ,3370,1650, 810 (NH 2 ), 1600, 1580, 1555, 1540, , 1470, 1460, 1280,1110,1090, 1070, 1025, 995, ), ,2910,1380, 1355 ( 2 ) (2, 2 ), (4, N'-CH 2 ), (4H,NH 2 ) 1.71 (4 2 ),4.11. (4, N'- CH 2 ), (4H,NH 2 ) (2 2 ), (2 2 ),4.13 (2, N'-CH 2 ), (2,N 2 2 ), (2, NH 2 ), (2, NH 2 ) 1.83 (4 2 ),4.41 (4, N 2 -CH 2 ), (4H,NH 2 ) ()-1,2,3,4-- 1,3-1,4-1, - (6:1), 1,1-1,2'- (XXI-XXIV). - 1,1'-: 1,5-(5- -1-)-3- (XXI), - (. 25). 1 -,. 1,2 -., -, [53], [55] (. 25). 158
95 25-2- (I-II) -3- (XXIII-XXIV) =1 (XXI, XXII); =2 (XXIII, XXIV) -, %*.,, D** R f ***,, -1 1,, XXI c (4H,N 1 -CH 2 ), 3450,3340, (4, NH 2 ) (NH 2 ), 1620, 1560, 1440, 1400, XXII ,1130,1100 ), c (2H,N'-CH 2 ), 4.88 (2, N 2 -CH 2 ), --) (2, NH 2 ), (2, NH 2 ) XXIII ,3330, ), 1605, 1560, 1545, 1470, 1440, 1290,1270,1160, (4, 2 ), (4, N'- 2 ), (4, NH 2 ) XXIV ,1045, (4, 2 ), 4.40 ), 1270, 1380,. (4, N-CH 2 ), ( 2 ), (2, NH 2 ),
96 --).. (2, NH 2 ) * 1 ** MNDO *** - : (1:1),,,,,,., - 5-, (5- (XII-XXIV) 26 H, 1,1-1,2-2,2'- (5- (XII-XIV) (5- (XV-XVII) (5- (XVIII-XX) (5--2- (XXI, XXII)
97 (5--3 (XXIII,XXIV) , 5-AT -, [109]: 5--1-, , -, 2 : 2ab : b 2 [109]. 1, - -., -.,,, (5- ). - 1,1 -, 2,2'-. 1, ,, S N 2, -,., -,, - 161
98 . 1, 10 3 [121], -, -. [137], [138], MNDO,, 5-. AMI [137], -. -,, - - [138].,, - [139] [72], 5- [140] 5- [141], -, -. [118] - - N(1) -. 5-AT, (21), - N(1) (22), N(2) (23) (24) (. 27,. 30). 162
99 ()- 1,2,3,4- ( AMI) , N(1) N(2) N(3) N(4) (5) N(6) , D 0, / _
100 , "- " (22), - N(1). - 5-AT: N(2) N(3), N(1) N(4).,,,,. -, -, - N(1), - 5-AT. 5-AT - N(1), -,, - N(1), N(4) N(2), N(3) (.. 27), N(1). 5-AT,, - N(2)., - 1,2-. 5-AT, - () -, 2, - - 1,1' (5), 2,2'-, -, - N(2)-. (5) (1,1-1,2-2,2'-),
101 - 1,2'-. - [142]., - - [143]. - [143].,
102 ,2,4-.,, -,, - - [144].,.,, -, -, -., [144], Fe (III), Co (II), Ni (II), Cu (II).,., Fe (III), [144], «-, -»., - Fe (III). Fe (II), [144],., - 1,.,, -. + N,».,, -,. 4- [145],,.,. NO
103 , -,. - Cu (II), [144]. [144],. ) [144]., -,,,, -., -., ;, -. -, -.,, [146] - : 1., , ,2,4- -1,2,4- [142], [147]-[158]. -,, 167
104 [142], [145], [147] ,2,4-. [] (NO 3 ) 2 0,2., =1:4 1:6 -. CuT 2 (N 3 ) 2 *0,5 2-1:2 [151]. [159]. [151] - 1,2, [157], 3,5- [158], 3,4,5--1,2,4- () [159]. () ,2,4-5 [160]. 5-, 3,5- [161]. H 2 PdX 4 (X=C1, ), 5-, 3,5- - (LH) 2 PdX 4 (L=L 1 L 2, L 3, X=C1, L=L 1, L 2 ; X=Br) (LH) 2 PdBr 2 (L=L 3 ). - <2, -, Pd(L)Cl 2 (L=L 1, L 2 ), Pd 2 (L) (L)Br 3 (L=L 1 L 2 ) [Pd 3 (L) 4 X 4 ]X 2 n H 2 O (L=L 3 ; X=l, n=3; X=Br, n=2)[161]. [156] 4--1,2,4-,, - ML 3 X 2 n H 2 O,, Ni, Cu, Cd, Zn. [162] 4,4'--1,2,4-, [163]. (- (AT) [10]-[15] ,2,4-,,, -. -,,, -,,. 168
105 , [156], 4-., -, (- ). - (d 7, d 8, d 9 ). - CuL 2 (NO 3 ) 2 * 0,5 2, Cu(II)., -., N 3 - -, CuL 2 (NO 3 ) 2 *0,5 2, , , ,. -, CuL 2 (N 3 ) 2 *0, [156], 4- -,. [156] - ML 2 X 2, 3, ML 4 X 2, -. [156], - -, -, NH C 2 v, -, ,. [156], ML 3 X : - Cu-N: -2,019, -2,101, - 2,327.,
106 [Cu(L) 4 (H 2 O)](C1O 4 ) 2., Cu-N 2,26-2,38., [156],. g >g II > 2,0,. -.,.., -, 0,1. [156]. [157], 5-. [131],, - :, , , -. -., -,. [158] 3,5-, - -. M:L ML 2 (NO 3 ) 2, - : ul(n 3 ) 2 ML 2 (NO 3 )
107 [161], 3,5- NH-N, -. [161] -, NH - NH , -., d 8. - d-d- 4-. : -,. CuL(NO 3 ) 2 -,, -,. CuL 2 (NO 3 ) 2, CuL(NO 3 ) 2. CuL 2 (NO 3 ) 2 16, , -., -. - d 9.,, -, - g--. [159] , -.,. -,, 171
108 Ni(TATP) 4 (NO 3 ) 2 *5H 2 O,. NH -, ( ). Ni -. - MN 6., -,,, -., Co(TATP) 6 (NO 3 ) 2 Ni(TATP) 6 (NO 3 ) 2, Co(TATP) 4 (NO 3 ) 2 -,. - [164]., 4, -, [159],, , -, -. (II) -1,2,4-., -. FeL 3 (N 3 ) 2, FeL 2 Cl 2, L-4. [155], - -.,. -, -, , 172
109 920, (II) N 1 N 2. -,,,,. =3-7 - Pd(L)Cl 2, Pd 2 (L)(L)Br 3, Pd(L)Cl (L=L 1,L 2 ). L=L 3 Pd(L)X 2 (X=C1, ), - [Pd 3 (L) 4 X 4 ]X 2 *nh 2 0 (X-C1, =3,, =2) [163]., [Pd 3 (L 3 ) 4 X 4 ]X 2 *nh 2 O. Pd, Pd - L 3, Pd. L 3 -, - N 1 N 2. Pd(L)X 2 (L=L 3 ; X=C1 - - ), - Pd(L)X 2, N 1 N 2,, Pd 2 N 4 "". Pd 2 (L)(L)Br 3 (L=L 1,L 2 ), Pd(L)Cl (L= L 1,L 2 ) N 1 N 2., -, [162 ]. - 4,4'--1,2, L 6 (NO 3 ) 6. -., - -1,2,4- : 173
110 1. - N 2 N 1, N 4, MX 2 L MX 2 L 6 (X-Hal). 3. 1,2,4-,. 3.2., - 3,3 -(5--1,2, ,3'-(5- -1,2,4-, [165]. [166] -.,, -. : -[3,3'-(5--1,2,4-)] (XXV), -[3,3'-(5-- 1,2,4-)] (XXVI), -[3,3'-(5--1,2,4-)] (XXVII), -[3,3'-(5--1,2,4-)] (XXVIII), -[3,3'-(5--1,2,4-)] (XXIX), -[3,3'-(5-- 1,2,4-)] (XXX), -[3,3'-(5--1,2,4- )] (XXXI), -[3,3'-(5--1,2,4-)] (XXXII), : R= ( 2 ); =0 (XXV), l(xxvi), 2(XXVII), 3(XXVIII), 4(), 5 (XXX), 7(I), 8(II). ( L 1 - L 8 ). (XXV - II) : - () ().,,,
111 28-3,3'-(5-- 1,2,4- (XXV, XXVI, XXIX, II) R 1 :(l): 2,. II - ),, % XXV - 1:2: XXVI 2 1:2: XXI 2 ) 4 1:2: II 2 ) 8 1:2: , - 105, - 95 ; (. 29) - (.31). -, 3,5- -3,3 -(5--1,2, ,5--1,2,4- -3,3 -(5--1,2,4- ) XXV, XXVI, XXIX, II, ,5- - 1,2, (. NH 2 ), 3320, (. NH 2 ), CH), 2990., ( NH), ( NH 2 ), 1580cp. (.; NH), (.), 1500.,1475., (.),-(.), ( NH 2 ), ( NH 2 ; NH 2 ; CH), - ( NH 2 ), (.; NH) - ( NH;.), 810. ( NH; 5.), (.; ) 175
112 (. NH 2 ), 3210 cp. (. NH 2 ), ), , ( NH), XXV NH 2 ), (.; NH 2 ), (.), 1500.,1480. (.),., (.), (.), ( NH 2 ),-( NH 2 ; NH 2 ; CH), 1110c. ( NH 2 ), (.; NH) 980 cp. NH;.), 810cp. ( NH;.), 740. (.; CH). XXVI (. NH 2 ), 3320 cp. (. NH 2 ), 3180 cp. CH), 2970., (v NH), 1665., 1650c. ( NH 2 ), (.; NH 2 ), ), 1430.,1465., 1415 cp. (.), cp (.), (.,-.), ( NH 2 ; CH), ( NH 2 ), (.; NH), 925. ( NH;.), 875. ( NH;.), (.; ). XXIX 3460 cp.(. NH 2 ), 3355 c.(. NH 2 ), CH), (. NH), ( NH 2 ), ( 4; NH 2 ), (), c.( ) (), cp.( ), 1220.,( NH 2 ), ( NH 2 ; NH 2 ; CH), ( NH 2 ), ; NH) ( NH; ), 855. ( NH; ), (; ). XXXII (. NH 2 ), 3340 cp. (. NH 2 ), CH), (. NH), ( NH 2 ), (; NH 2 ), 1555 cp i. (), (), () (), ( NH 2 ), ( NH 2 ; NH 2 ; ), ( NH 2 ), (; NH), 930.( NH; ), ( NH; ) 745.( ; ). [50]. 176
113 30 177
114 - 1,2,4- [70], [92], [166]., ,, (XXV-XXXII) -, : , , , , () NH , NH , ,, -.,, "" - 2 -,., , , [167]., , 2., - - 1,2,4-: , , , ,
115 - [168], [169]. 31-3,3 -(5-) XXV, XXVI, XXXII,. XXV ( 100), 124(18), 123(0,1), 98(32), 97(11), 71(5), 69(6), 57(10), 55(7), 45(9.1), 44(21), 43(20), 42(7), 29(5), 28(50), 27(6), 18(36). XXXVI XXXII 222( 47), 193(11). 166(5), 165(6), 125(15), 124(4), 113(5), 112(82), 111(100), 98(183), 97(4), 58(5), 57(4), 56(3), 43(7), 41(5), 32(41), 28(55), 8(65), 17(1 2). 278(,24), 240(12,5), 72(7), 221(2), 209(5), 196(3), 195(5), 182(13), 181(100), 168(19), 167(13), 154(8), 153(48), 140(8), 139(14), 126(6), 125(29), 112(38), 111(95), 99(14), 97(14), 69(8), 58(10), 57(11), 55(14), 43(14), 41(14), 28(19), 18(14). -, %. XXV, - [168], [169]. XXVI - =180 (.31), -. - =97,98., [170]. XXXII -, -,, (= %). - =
116 , [163]. =183.,, -. II. XXX, -, -.. : =249,235,193, -, , 3 7 -, , - =97-195, - (M/e 98, 112, 137). =151, -, - C 9 H 19 -,,. =209,,, (5) -. = , -,, -.,, - [M-R] +, -, -,, [171] Fe (III), Co (II), Ni(II), Cu(II) -3,3'-(5--1,2,4-), - [142], : - n ml -,. 180
117 Fe(III) Fe(III) 1,2,4-- [172], [173]. - Fe(III) : 5- (L 1 ), 4-ATP (L 2 ), 3,5- (L 3 ), -[3,3'-(5--1,2,4-)] (L 4 ) -[3,3'-(5-- 1,2,4- (L 5 ). XXXIII-XXXVII -,,,. 32, Fe(III) 1,2,4- - ), % Fe N, XXXIII 6 13 N 15 O / 10.8 XXXIV C 3 H 5.5 N 9 O 9.5 Fe 16.5/ 16.7 XXXV C 6 H 16 N 18 O 9.5 Fe 10.3/ XXXVI C 4 H 11 N 12 O 9 Fe / 12.5 XXXVII C 5 H 13 N 12 O 8.5 Fe 14.4/ / / / / / / / / / / / / / / / ,. ( L 1 - L
118 182
119 - [142]. [164], - N-. [92] 1,2,4-. : (L 1-4 ), (L 5 ), 1450 (L 1 ), (L 2 ), (L 3 ), (L 4 ), (L 5 ); 1245 (L 1 ), 1200 (L 2 ), 1220 (L 3 ), 1225 (L 4 ), 1295 (L 5 ) L l - L 5 - XXIII-XXXVII L 3 < L 1 < L 2 ( ) L 1.,, L , , - XXXIII, XXXIV XXXV., [170] - L (L 2 ) [174], [154],,, L 2, L 1,,, - L 2 N(1) N(2). - L 2 - [174]. L 3 L 1, - [158]. XXXVII, , ; u - 183
120 [175]. - Fe-N XXXVI, XXXVII XXXIII-XXXV, (. 32). [170], XXXVI, XXXVII N(4) -,, L 4, L 5., - [13], L 4, L 5 N(4) N(4'). -. -, - 1,2- (- ) L 5 XXXVII, -. 31) : 1- L 5, 2 - XXXVII XXXVII - ( 2 %), , (31 %). 184
121 360. L 4, L 5, - [13]. XXXIII XXXIV - - ( =1.8.). XXXVI XXXVII -. -, -. XXXV ( =2.7.) - (III) -. - XXXV C ( )..32. XXXV XXXV, d- "" " - [176]. -,
122 . XXXVI, -,. -, "",., XXXVI -. - [177]., XXXVI, XXXVII,.,, [177] 3,4,5-1,2,4- Fe (III), () [178]. (II) 4- FeL 3 A 2 mh 2 O, -1,2,4-, L=4-ATP, A-NO 3, m= Fe(II) N(1) N(2) -. -N-N-,. - -, FeN 6. -., Fe(5- ATP) 3 (NO 3 ) 3 Fe (4-) , 310 = , 305, 31, ,3 -(5- Co(II), Ni(II) - AT [12]. - XXV, XXVI, XXIX, XXII : [3,3'-(5--1,2,4-)] [3,3'-(5--1,2,4- [3,3'-(5--1,2,4- [3,3'-(5--1,2,4- (XXXVIII) (XXXIX) (XL) (IXL)
123 [3,3'-(5--1,2,4-)] [3,3'-(5--1,2,4-] [3,3'-(5--1,2,4- [3,3'-(5--1,2,4- (VIIIL) (VIIL) (VIL) (VL) VIII-VL [L(N ) 2 ] nh 2 O; VIL, VL [NiL 2 (NO 3 ) 2 ] nh 2 O, VIIIL, IXL [NiL(H 2 O)(NO 3 ) 2 ] (II) Ni(II) XXXVIII -, 3, : - N * ,24/ 13,75 1,70/ 1,72 42,03/ 40,11 17,46/ 16,91 XXXIX ,95/ 16,52 2,28/ 2,20 39,72/ 38,57 17,03/ 16,25 VIIIL ,21/ 23,70 3,65/ 3,46 35,68/ 34,57 15,01/ 14,57 VIIL ,25/ 31,30 4,23/ 4,78 32,10/ 30,43 12,65/ 12,83 VIL ,79/ 18,64 2,36/ 2,33 49,75/ 48,93 10,83/ 11,45 VL ,16/ 22,10 2,91/ 2,95 48,15/ 46,41 10,75/ 10,
124 IVL ,91/ 22,70 3,69/ 3,78 35,02/ 33,10 14,41/ 13,95 IIIL ,68/ 31,75 4,28/ 4,81 33,03/ 32,90 12,55/ 12,95 *., Fe(III), ,, ,,, -., -. -,, - -, ; -, u(ii) (II) VI-III: [3,3'(5--1,2,4-)] (IVL), [3,3'(5--1,2,4- (IIIL), [3,3'(5--1,2,4- (IIL), [3,3'(5 --1,2,4- (IL), [3,3'(5--1,2,4- (L), [3,3'(5--1,2,4- (LI), [3,3'(5--1,2,4- (LII), 188
125 [3,3'(5--1,2,4- (LIII) IVL, LIII,,,, 13,. [142]. - - [179]-[182]. - [183]. [183], 4,4'- - Fe (III). Co(NCS) 2 (Btr) 2 2, Btr -4,4'-- 1,2,4- [162]. [162] 1,2,4- : () : - -, ( ) 5., ( ) ,2,4-, -. [157] 5--, u(5-) 1,5 (N 3 ) 2., 5-,, (), - (260, 320, (), 775(), 860, 915()) ,. - 1,2,4-, - 189
126 [142], [152]., [173] -,, , , [142]. Cu(3-ATP) 1,5 (NO 3 ) 2 5- [157]. M-L ( ). - 5-,, - [157], [180]. ( ), -, [157]., , [159] N "". N(4) 5- [142] , NH- [10],.. NCV, CIO/ [125]. () (II) [145]. [184] 1,5-., (1035,1270, ) NO 3 - u(ii). ( IL, LIII) , , [185]. 3300, [160]., - [142]. - 5-V-XXXII - 190
127 , [92], [97], 1,2,4-. [92], ; , ; ; XXV-II - H 2, ( ), ( N 2 ( )..,, - - (-1620, , ). - ( ) - -., NH 2 (. IVL, LIII), (. IIL-IL) (. LI-LIII) L 1 L 2, = 0.2, L 2-30 [13]., - (. LII, LIII) - [186].,,, - "" ( Å) [186]. XXV-II , - IVL-LIII "" 4 [160] [180]-[182]., ,,,, 191
128 ., NO 3.,,. - L,, - NH 2. -, - (. 3.2) ( ) ( ),,., (II)., - -, u(ii) N(4), N(4'). (- ) 1,2,4- Cs - -., (- N 6 ) 4,4'--1,2,4-, 1,1 - Cs [162]., 5-, AT XXV-II IVL-LIII - AT ( ). -. Cu(II) 4--1,2,4- (g 2.24, g 2.05) [175]. 1,2-- ; -. [187] -()- -) (II)], -,. [161],,
129 ,. - 4 N 4 ). g-u(ii) 5- (1:3, 4.3) g 2.27 g ), [177]. -, [181]. [CuT 3 ](NO 3 ) 2 0,5 2, CuT 2 (NO 3 ) 2 0,5 2,, u(ii). g- (gcp=2.118) [145]., -,, -., [185] PC-. u()(n 3 ) 2, -,. - u(ii). - 1/ () [158]. [158], - Cu(II), -., Cu(II),.. ) CuL 2 (NO 3 ) 2 (L=1,5-) ( = 1.83.). ) [184]. - ), -., - [187]. [149], 2 2L -., - - [185]. 193
130 IVL-IIL. IVL IIIL g, g-, [188], g ~ 2.24 g ~ 2.06; ,. -.,,,, -, u(ii), - (d 9 ). IIL g- (g ~ 2.09, g -2.02,,,., IVL - IIL, - ( R ( 2 ) 2 ). (IIIL) -., IVL ,2,4- (4-) u(4-tp) 2 (NCS) 2 [170]. [170] IVL, 4-, 1,2--,. - un 6 =1.86)., L 2, =5.0 Å, =3.3 Å, c=7.1 Å,. Cu(AT-2) 2 (NO 3 ) 2 XXVI., Cu -. - (3,5 Å), -. u., 8 Å. (II) L 2 NO 3. Ni., -. L 8 194
131 , u(n 3 ) 2.,,. XXV -,.,,., -., /2=3,5 Å... - (20-55 ) - (2,5 %), (. 35). ( ), %, 35 %.,.,,. 24 %, - 26 %. IL-1V 35 -,, IL I II ± ±
132 L I II ± ±4.3 LI I II ± LII I II ±3.2 LIII I II III ± ± ±2.8 XXVI 0,5 % 353 ). (403 ) (0,5 % ). 16 % (422 ) L 2. -,. - ( 433 )., 9 % - (R). (573 ) () - ( ),. L 3 (XXVII),, -., ). - L 2, (II 533, III 613 IV 736 ). -. IIIL IIL -,, -., -. IIIL L 2, I -, , - ( 196
133 ). II - ( ) 49 %, ul(n 3 ) 2 -,, IIIL -, (TG), 18.0 % ; 17.4 %. IIL. -,. I , II II 1,5. 16 % (G-13,6 %)., : 1. ul(n 3 ) 2 - CuN IVL-IIL. ( ), IVL L 1 - L 3. ( 2 ) IVL-IIL. -,. : (CuL(NO 3 ) 2., (154.), -. L 1 - L 3 (165.), - ( IIL)., : 1. : CuL(NO 3 ) 2 (,, 13, ). 2. CuN 4 (,, ). 3. v N(4), N(4') : -. - : 1. :, - Ni 3 )(N 3 ) 6 2 0)
134 2. 1,2-1,1 '-. N(4), N(4'),, - N(1), N(2) 3. : -,. (1,2,4- TP) 2 (NCS)2 [163]. IVL-LIII - - CuN 4, - Cu(II)., L 5 (- ) g- (), -., (IL) - CuN N 3 - [185]., - -, -,
135 ,2,4-5--1()- 1,2,3,4-,,. - -,. - [189], [190]. -,, ). -., - 1,2,4- () ,2,4-,,, - -., - (),.,, -, [90],. - 5-,, - -,
136 , - : I. : II. :. 5- [94]:
137 , - [191], -. [77], 5-- 1,2,4-, N--3(5)--1,2,4-: ,2,4-,, - [77], [191], [192]:, [77], [191] - NH R., -, -,,.,,,., [193], N- :
138 ,, "- " "" -, :, 5- " "". - 1,2, , NH-, NH 2,,, [194]. -., - ( 1),,., -, ,2,4-,,.,,, 1,2,4- [90], [195], [196],,
139 - [197]:, -. -,,,. -, -, -.,, - -,. - -,, -, [198] ,, () [191], -,. -. -, ( ), - 5-.
140 , , " " )[191], [196]. [53], 1,2,4-,. -. ("") 1,2,4-,, - -,. "- ".,, (,.) ("") -,,. "" - "",., , [166], [199]. - -COCI -,. "" - ),,,. -, -.
141 , - - -,, [166], [199]., -, -,, -,. 4.2., 1,2,4-5--1()-1,2,3,4-, - 1,2,4-5- [87], [198]-[206]. 5-., - 5-, - [207]. - : (),, 1,2,4- -, , [208] ,2,4-, 3 5 [209], [210]., -,, - [209], [210]. -1,2,4-, [205] -4--1,2,4- [211].
142 [212], - -1,2,4--. [213], [214], -1,3, ,2,4-,.,, ( ) - [215]-[227] ,2,4-1,2, ,2,4-, ,2,4-, , ,5-- 1,2,4-, ,2,4- [217]-[221]. [217], [218], [220], [221] -, -,,., -,,, ,2,4-- -,, -. [95], -, [206]., , -,, -, - [223]. - () -
143 [62], [228]., -,,,, [62], [229]. -, , - - S N 2, [87]. -, , - [225]:, -,, -, -. -
144 ., - [87]., -, [87], [229]. -. [212].,, [87], - [229], [191], [226] ()-1,2,3, ,3,4- [129]. 5-, [90]. 5- [207]. - -, 1,3,4-. -, N--2- (0,5 %-) 0,2.,, 2, - 1,3,
145 , -.,, -, - «-» «-» [191] , -, -,., - [191]. ( LiCl) [87], [191], [229]. - -,. - [87], [191]., ; -, - [191]..
146 , ( ) [230]., - [230]. -,,., - - [87]. - - (15-25, - ). - - [244], [248]., -,,,., - -.,, - - [178], [218],,, [226], [227], [230]. [232] [232]-[234]. [235]. - (= ) l 4 (= ). [235]. - : -, -,,,., -
147 : [236], - [236], [237]. - (NaOH, ) [236], 237]. -, [234], [236], [237], () [238]., [233], [235], - [234]-[237] "" -. -,,. "". - [191]. - [239],,,., [240],, [241], [242]. - [241], [242].
148 [239], [241]., - -, - [241],,, [239]. - [239] ,, ,3-(5--1,2, ,2,4-. - [242] LV-LIX 3,5- (LX), AT XXV, XXVI, XXIX, XXXV () " " :
149 =0, R= NH 2 (R LV= NH; R, R" -); n= 0 (LVI); n=l (LVII); n=4 (LVIII); n=8 (LIX). : (3,5- -1,2,4- (LV), [3,3'--(5-- 1,2,4-)] (LVI), [3,3'--(5--1,2,4-- )- (LVII), [(3,3'--(5--1,2,4-- (LVIII), [3,3'--(5--1,2,4-) (LIX).., - ( ),. LV-LIX ,. : -, -. - [239] [242]. - [239], [242] -, , ,
150 , [239], [241] -,, %.,.., - [239], [241]. LV-LIX,.. -.,. : - [241] LV-LIX LV-LIX 1 NaOH (2:1). : -
151 , -, -.. LV,. [242],., "" "", - - ( HCI) - (). - : (3,5--1,2,4-) - (LX), [3,3'--(5--1,2,4-)] (LXI), [3,3'--(5--1,2,4- LXII); - (LXIII, LXIV, LXV), (LXVI, LXVII, LXVIII) (LXIX, LXX, LXXI). ( ) ). ( 3-4%.). 1,2,4-,..,,,, [240] ,.
152 . 35. (LV, LVI, LVII, LVIII, LIX) ( ) 20 - ;, - (5-15 ) -. "- ",. "- - ", "" 20., [243] -, , (- ) -, [191].
153 LX, LXI, LXII -,, (LX, LXI, LXII). [24].., - -, - LX, LXI, LXII (. 37). -.
154 . 37. LX, LXI, LXII (C = C = 0.05, t = 20 ), - - (NaOH), - NaOH 2 1, [88], [191], [242]. (),, -, , -, -,. -,
155 . [87], [243],. LX, (LXI), (5--1,2,3,4- ) (LXXII). 0.5 (94.8 %), (93.3 %) , - -, -.,. - 20, " - - " LX, LXI, LXXI LX, LXI, LXII = = 0.1, t = 20, n=1000 )
156 -, ( ) - LX, LXI, LXXII. LX, LXI, LXXII LX, LXI, LXXII, , - - [87], [236], [242] ,, , -
157 ,, -. 3,5- XXV ( ) -. [87], [242]-[244] -,., -,. +18± LX, LXI, LXXII LX, LXI, LXXI -,, -. -,., -
158 : 0,2, - +18±2. (.40),,, -., - " - ". -, - -., - (- l). - LX, LXI, LXXI 73, %. - 1,2, ,2,4-36 * -, () ( ),./,,., % L (0.15) (0.15) (0.30) 98 ± LI ± (0.03) (0.03) (0.60)
159 LII ± (0.03) (0.03) (0.60) LIII ± LIV 8.35 (0.03) LVII 5.05 LVIII H +LiCl LIX / LX / LXI +LiCl LXII / LXIII +LiCl LXIV / LXV +LiCl LXVI / LXVII / (0.06) 5.95 (0.06) 2.97 (0.03) 1.66 (0.01) 5.41 (0.03) 1.80 (0.01) 6.67 (0.03) 2.22 (0.01) 8.35 (0.03) 2.78 (0.01) 1.92 (0.01) 3.81 (0.03) (0.06) (0.06) 7.32 (0.04) 2.01 (0.011) 5.49 (0.03) 2.01 (0.011) 5.49 (0.03) 2.01 (0.011) 5.49 (0.03) 2.01 (0.011) 2.01 (0.011) (0.60) 98 ± (0.04) (0.11) (0.11) (0.11) (0.11)
160 LXVIII 5.05 (0.06) (0.06) LXIX +LiCl 5.95 (0.06) (0.06) LXX / 0.99 (0.01) 2.39 (0.01) (0.10) LXXI / 1.66 (0.01) 2.39 (0.01) (0.10) LXXII +LiCl 5.41 (0.03) 7.17 (0.03) LXXIII / 1.80 (0.01) 2.39 (0.01) (0.10) LXXIV +LiCl 6.67 (0.03) 7.17 (0.03) LXXV / 2.78 (0.01) 2.39 (0.01) (0.10) LXXVI / 1.92 (0.01) 2.39 (0.01) (0.10) LXXVI 5.95 (0.06) 9.30 (0.60) LXXVII +LiCl 5.95 (0.06) 9.30 (0.06) LXXIX / 0.99 (0.01) 1.55 (0.01) (0.10) LXXX / 1.66 (0.01) 1.55 (0.01) (0.10)
161 XIXC +LiCl 5.41 (0.03) 4.65 (0.03) XVIIIC / 1.80 (0.01) 1.55 (0.01) (0.10) XVIIC / 2.22 (0.01) 1.55 (0.01) (0.10) XVIC +LiCl 8.35 (0.03) 4.65 (0.03) XVC / 1.92 (0.01) 1.55 (0.01) ,,., (),., - [55],. ( ) (), 5-,., (LiCl) : - [191] ,2, ,2,4-1,2,3,4-
162 [37], [93], [193], [195], [218], [245]-[247], -1,2,4- - (), - : () [90], [191], ( -I) [218], [244]-[246],., [248] "" () [37], [193], [195], [247], (-I) [37], [93]., - -NH-CO-, - [93, [245]., [242, [249], -, -,. 1,2,4-- -, 5- -1,2,4- ( ) () (. 41).
163 . 41. (3-- 1,2,4-) ( ,2,4-), -NH-CO- ) N--(). -, [250], -,,., -,. -, [69], [92], [251], - - [249]. - [92, [251]. -, -. =0 - (-I)
164 -II -III ( CN, NH, OCH, CO ) N , , - 1,2,4- ( CO )., (. 37) - - [92], [99], [252]. 37 1,2,4- ( 1 ) - -. NH - -, L 2950 c LII LVIII ) 2 ) ) ) 745.
165 LXII ) ) 733. LXIV LXVI LXVIII LXX LXXII LXXIV LXXI XIC c c c XVIIIC ) ) ) ) ) ) ) ) ) ) ) ) ) ) )
166 , - N-H -. NH , [167]. - - [92], [252]. : -. - NH , - [96], [252] = ( CO ); , II. -III, -, =0 N-H, [46],, -I -II., -,. -IV -V -, NH
167 : 1. 5-; ; ; )
168 . [92], [253], 1,2,4- -,, -., ( ), -, [92], [93], [247]., - : ; ; ; [99], [253]-[255]., IXL-VL -,. -, -, [254]. [93], [254],, ,2,4-.,, [13], AT XXVI , - N. 1660, =0 - -I II, -, OCN NH,. -III, -, OCN NH, ,, -I -II.. -
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