Диссертация (1150306), страница 10
Текст из файла (страница 10)
>4##,+2 "*'*+& +.#5)#J %),#)+%F)*+,% b(C`N)."!#100; +"#1,.&3 AOG 1- +*#5%)#)%J 75–78 % 91–94 %4#T,+2 5F& +%)/'#,& F +%'()*4 "*'# *,5F:3 /.:"" NMe2 (:78?AED 22), F ,* F.#42 1&1 F +"#1,.&3 +*#5%)#)%J 79–82 % 95–98)&9'T5&T,+2 5F& 4:'(,%"'#,&, F 1*,*.H3 9*'## +'&9*"*'()HJ +%/)&' *,)*+%,+2 1 &,*4&4F*5*.*5& N(CH2)2 *9#%3 )#^1F%F&'#),)H3 /.:"", & 9*'## +%'()*"*'()HJ 4:'(,%"'#, *,)*+%,+21* F+#4 *+,&'()H4 &,*4&4 F*5*.*5& F &'%K&,%0#+1%3 $#"23. ; +"#1,.&3 +*#5%)#)%J 75–82 %) (%)91–98 ,&1Y# ".%+:,+,F:T, 5F& :S%.#))H3 +%)/'#,& F +'&9*4 "*'#, *,)*+2M%#+2 1 &,*4&4!(N=C)F*5*.*5& /.:"" NH (:78?AED 22). !%/)&' F 9*'## +'&9*4 "*'# +**,F#,+,F:#,&,*4:"#$%&F*5*.*5&&4%5.&I*)*F*J 0&+,% 4*'#1:'H, 9*'## +%'()*"*'()HJ +%/)&' *,)*+%,+2 1 %4%)*/.:""#. ;!(N–()!(C–()2)#1*,*.H3 +':0&23 F +"#1,.&3 )&9'T5,+2 +"%)-+"%)*F*#+ 1*)+,&),*JJPtH,!(N=C)!(N$C=O)F&%4*5#J+,F%#%&%'.&F)*J034 X$, 3&.&1,#.)*J 5'2 1**.5%)%.*F&))H3 1 "'&,%)#(II) %4%)*F [27, 99]. !%/)&'H/%5.&I*)*F*J3600/.:""H NMe2 F +"#1,.&3 1*4"'#1+*F$&–175–78 +4#M#)H F 9*'## +%'()*# "*'#600)&~0.2 4.5.
"* +.&F)#)%T + +**,F#,+,F:TM%4% +%/)&'&4% F +"#1,.&3 +*#5%)#)%J 91–94, 0,*4*Y#, 9H,( *9_2+)#)* ^1.&)%.:TM%4 ^KK#1,*4 $%&)&,)*/* '%/&)5&. !"#1,.H AOG 1- %*))H3+*#5%)#)%J [68]Cl–[74]Cl, [99]Cl &)&'*/%0)H +"#1,.&4 [32]Cl % [33]Cl (:78?AED 14), & +"#1,.+*#5%)#)%2 100 &)&'*/%0#) +"#1,.&4 F#M#+,F 34 % 35, *"%+&))H4 F /'&F# 3.; 4&++-+"#1,.&3 )#%*))H3 +*#5%)#)%J 75–82 % 91–98, +)2,H3 F "*'*Y%,#'()*4 .#Y%4#,)&9'T5&T,+2 +**,F#,+,F:TM%# "%1% 1F&I%-%*)*F [M + H]+, & ,&1Y# "%1% [M + Na]+, [M + K]+,[2M + -]+, [2M + Na]+ % [2M + K]+. 8*4%4* ^,*/* F +"#1,.&3 %4#T,+2 K.&/4#),)H# %*)H [M –Cl]+ (75–82, 91–98), [M – NCO]+ (75–82) % [M – NCO – Cl – H]+ (75–82).
?9)&.:Y#))HJ ,%"K.&/4#),&$%% 3&.&1,#.#) 5'2 3'*.%5)H3 1*4"'#1+*F "'&,%)H(II) [88, 102].!!60!!"#ClHNNo-CHN(CH3)2ClPtNNN(CH3)2NHCH3!-CHNHNH9.02.0!. ".(78?AED 22. !"#1,. AOG 1- F#M#+,F& 91.; 4&++-+"#1,.&3, +)2,H3 F *,.%$&,#'()*4 .#Y%4#, )#%*))H3 +*#5%)#)%J 75–82 % 91–98)&9'T5&T,+2 +**,F#,+,F:TM%# "%1% 1F&I%-%*)*F [M – H]– % [2M – H]– (75–82, 91–98), & ,&1Y#[M – NMe2]– % [2M – NMe2]– (91–94). ; 4&++-+"#1,.&3 %*))H3 +*#5%)#)%J [68]Cl–[74]Cl, [99]Cl% [83](#-CH3C6H4SO3)–[90](#-CH3C6H4SO3) )&9'T5&T,+2 "%1%, +**,F#,+,F:TM%# 1&,%*): [M –Cl]+([68]Cl–[74]Cl,[99]Cl)%'%[M – #-CH3C6H4SO3]+([83](#-CH3C6H4SO3)–[90](#-CH3C6H4SO3)), & ,&1Y# K.&/4#),)H4 %*)&4 [M – NCNR2 – Cl]+ ([68]Cl–[74]Cl, [99]Cl).G#I:'(,&,H ^'#4#),)*/* &)&'%I& F+#3 "*':0#))H3 1*4"'#1+*F +*/'&+:T,+2 + .&+0U,)H4%5&))H4% 5'2 ".#5"*'&/H3 +,.:1,:..O*'#1:'2.)H# +,.:1,:.H 76, 78, 81•2MeNO2, 82•MeNO2, 91•MeNO2, 92, 94 %95•MeNO2•H2O ".#5+,&F'2T, +*9*J 1**.5%)&$%*))H# "*'%^5.H + ,%"%0)*J "'*+1*1F&5.&,)*J 1*)K%/:.&$%#J (:78?AD7 25 % 26).
;+# :/'H F*1.:/ 4#,&''*$#),.& "'&,%)H(II)9'%I1% 1 90º. G&++,*2)%2 Pt–Cl )&3*52,+2 F %),#.F&'# 2.016(2)–2.0271(15) Å % 2F'2T,+2,%"%0)H4% +F2I24% PtII–Cl [89]. G&++,*2)%2 Pt–N%4%) [1.955(5)–1.9844(15) Å] 3&.&1,#.%+,%0)H5'2 1**.5%)%.*F&))H3 1 "'&,%)#(II) %4%)*F [117], & 5'%)H +F2I#J Pt–N/%5.&I*) [2.016(2)–2.0271(15) Å] 2F'2T,+2 3&.&1,#.%+,%0)H4% 5'2 +F2I#J PtII–N(sp2) [89]. !F2I% Pt–N$%&)&,, 5'%)H1*,*.H3 )&3*52,+2 F 5%&"&I*)# 2.005(2)–2.071(4) Å, 0,* )&9'T5&'*+( .&)## 5'2 $%&)&,)H31*4"'#1+*F "'&,%)H(II) [119].!!61!767881 •2MeNO282 •MeNO2(78?AED 23.
O*'#1:'2.)H# +,.:1,:.H $%&)&,)H3 1*4"'#1+*F.91 •MeNO2929495 •MeNO2•H2O(78?AED 24. O*'#1:'2.)H# +,.:1,:.H 5%3'*.%5)H3 1*4"'#1+*F.!!62!='%)H +F2I#J C–N%4%) % !–N/%5.&I*) +**,F#,+,F:T, 5F*J)H4 +F2I24 C=N % )&3*52,+2 F5%&"&I*)# 1.294(2)–1.300(4) % 1.299(6)–1.306(3) Å +**,F#,+,F#))* [90]. ; ,* Y# F.#42 &4%5)H#+F2I% N–(C=N)%4%) % N–(C=N)/%5.&I*), & ,&1Y# +F2I% C–NR2 +**,F#,+,F:T, *5%)&.)H4 +F2I24 !–N [1.370(8)–1.385(2), 1.363(8)–1.374(6) % 1.340(2)–1.376(8) Å +**,F#,+,F#))*] [90].
;+*#5%)#)%% 81 .&++,*2)%# 4#Y5: &,*4*4 C(13) % N(3), .&F)*# 1.143(9) Å, +**,F#,+,F:#,)*.4&'()*J +F2I% C`N [90]. ; 1*4"'#1+&3 76, 78, 81 % 82 .&++,*2)%2 C–N % C–O F $%&)&,)*4'%/&)5# )&3*52,+2 F %),#.F&'&3 1.070(5)–1.159(4) % 1.196(8)–1.219(4) Å +**,F#,+,F#))*, 0,*3&.&1,#.)* 5'2 N-1**.5%)%.*F&))H3 $%&)&,*F [119-124]. G&++,*2)%2 N–N [1.426(7)–1.449(2) Å]2F'2T,+2 ,%"%0)H4% *5%)&.)H4% +F2I24% N(sp2)–N(sp3) [90].; 4*'#1:'2.)H3 +,.:1,:.&3 76, 78, 81•2MeNO2, 82•MeNO2, 91•MeNO2, 92, 94 %95•MeNO2•H2O 1*'($& (1,3,5-,.%&I&"#),&5%#))PtII %4#T, "*0,% "'*+1:T /#*4#,.%T.
;+# :/'H F5&))H3 4#,&''*$%1'&3 9'%I1% 1 120º, I& %+1'T0#)%#4 :/'*F (N=C)%4%)–N–(C=N)/%5.&I*),)&3*52M%3+2 F 5%&"&I*)# 127.95(11)–130.0(5)º % N–Pt–N, 9'%I1%3 1 90º. c-!%+,#4H&.*4&,%0#+1%3 1*'#$ % 4#,&''*$%1'*F )# +*".2Y#)H, ,*.+%*))H# :/'H 4#Y5: +%+,#4&4%.&F)H 70.00–88.84º.C**.5%)&$%*))HJ "*'%^5. +*#5%)#)%2 62 (cO9P< 24) %4##, *1,&^5.%0#+1:T /#*4#,.%T+ 3-$-1*)K%/:.&$%#J ,.%5#),&,)*/* '%/&)5&. ;+# :/'H F*1.:/ 4#,&''*$#),.& "'&,%)H(IV)9'%I1% 1 90º, I& %+1'T0#)%#4 :/'& N(3)–Pt(1)–N(1), .&F)*/* 80.2(2)º.
G&++,*2)%2 Pt–Cl)&3*52,+2 F 5%&"&I*)# 2.3077(14)–2.3193(14) Å % 2F'2T,+2 ,%"%0)H4% 5'2 +F2I#J PtIV–Cl [16,21, 24, 89]. ='%)H +F2I#J Pt–N(1) % Pt–N(6) .&F)H 2.000(4) % 2.012(4) Å +**,F#,+,F#))* %2F'2T,+2 3&.&1,#.%+,%0)H4% 5'2 %4%)*F, 1**.5%)%.*F&))H3 1 "'&,%)#(IV) [16, 21, 24]. !F2I(Pt–N(3) [1.959(5) Å] )#4)*/* 1*.*0# +F2I#J Pt–N(1) % Pt–N(6), 0,* 4*Y#, 9H,( *9_2+)#)*)&".2Y#)%#4 F +F2I23 F 9%$%1'%0#+1*J 0&+,% 4*'#1:'H. G&++,*2)%2 N(1)–C(1) % N(3)–C(4).&F)H 1.292(6) % 1.257(7) Å, 0,* 3&.&1,#.)* 5'2 5F*J)H3 +F2I#J C=N [16, 21, 24, 90].X.:""H NMe2 '#Y&, F *5)*J "'*+1*+,% + 9%$%1'%0#+1*J +%+,#4*J % +F2I% N(2)–C(1),N(4)–C(4), N(5)–C(11) % N(6)–C(11) (1.324(7), 1.317(8), 1.348(6) % 1.327(6) Å +**,F#,+,F#))*)%4#T, ".*4#Y:,*0)HJ "*.25*1 4#Y5: *5%)&.)*J % 5F*J)*J +F2I24%.
!F2I% O(1)–C(1)[1.359(6) Å] % N(4)–C(11) [1.358(7) Å] 2F'2T,+2 *9H0)H4% *5%)&.)H4% +F2I24%, F ,* F.#42, 1&1+F2I( O(1)–N(3) [1.520(6) Å] +'#/1& 5'%))## +.#5)#+,&,%+,%0#+1%3 I)&0#)%J [90].!!63!4.6 M<DHX@9A798*':0#))H# F 5&))*J /'&F# .#I:'(,&,H 4*Y)* +K*.4:'%.*F&,( F 5F:3 "*'*Y#)%23.-&4% 9H' *9)&.:Y#) #MU *5%) ".%4#. ,*/*, 0,* 5%&'1%'$%&)&4%5H %4#T, *,'%0):T *,):;.,;& )%,.%'*F .#&1$%*)):T +"*+*9)*+,(. ; 0&+,)*+,%, 9H'& *9)&.:Y#)& .&)## )#%IF#+,)&2"#.#/.:""%.*F1& 4-1&.9&4%5%)&4%5*1+%4*F F &4%5.&I*)H, ".*4*,%.:#4&2 "'&,%)*J(II), %%I:0#) #U 4#3&)%I4.
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pH-I&F%+%4H3 'T4%)#+$#),)H3 +F*J+,F % %3 1&,&'%,%0#+1*J &1,%F)*+,% [39, 117, 127].8*4%4* ^,*/*, +*#5%)#)%2 75–98 2F'2T,+2 )*FH4 ".%4#.*4 "'&,%)*FH3 1*4"'#1+*F,+*5#.Y&M%3 1**.5%)%.*F&))H# &,*4*4 N(sp2) /%5.&I*)*F*J /.:""H &4%5.&I*)H.
>IF#+,)H#&4%5.&I*)*FH# 1*4"'#1+H "'&,%)H(II) %4#T, %)H# +"*+*9H 1**.5%)&$%% '%/&)5& (:78?AED 25,B % C) [128-133].HNR2NPtNHANNR2ArPtH2NNPtRHNNRHNR'BH2NR'C(78?AED 25. ?"%+&))HJ F 5&))*J /'&F# (") % .&)## %IF#+,)H# (0 % !) +"*+*9H 1**.5%)&$%%&4%5.&I*)*F 1 "'&,%)#(II).; )&S#4 +':0, +,&9%'%I&$%2 S#+,%0'#))*/* 4#,&''*$%1'& *9:+'*F'#)& ".%+:,+,F%#41&.9&4%4%5*%'()*/* K.&/4#),&, 1**.5%)%.*F&))*/* 1 4#,&''*$#),.: % +"*+*9+,F:TM#/*3#'&,%.*F&)%T.!!64!+2"0" 5a$!&'(,3'#%"26#"N 4"!%65.1 57R7@98D79 7 T7R7DE-O7P7@98D79 P9;EGB 788H9GEF<A7>,AT:<D:<8AB9 8Q9D;:B F *9'&+,% 4000–400 +4–1 9H'% I&"%+&)H )& +"#1,.*4#,.#Shimadzu FTIR-8400S F ,&9'#,1&3 KBr. !Q9D;:B N3( 1# 713!{H} 9H'% %I4#.#)H )&+"#1,.*4#,.# Bruker DPX300 ".% 25 ºC.
R%4%0#+1%# +5F%/% ".%F#5#)H *,)*+%,#'()* +%/)&'*F%+"*'(I:#4H3 .&+,F*.%,#'#J: 5'2 AOG 1- – CDCl3 (7.26 4.5.), (CD3)2CO (2.05 4.5.), (CD3)2SO(2.50 4.5.); 5'2 AOG 13! – (CD3)2SO (39.52 4.5.). 3<88-8Q9D;:B FB8EDESE :<R:9W9A7> 9H'%"*':0#)H )& ".%9*.# Bruker micrOTOF, *9*.:5*F&))*4 %*))H4 %+,*0)%1*4 ,%"& ^'#1,.*+".#J(Z!>). ='2 ".*F#5#)%2 4&++-+"#1,.*4#,.%0#+1%3 %++'#5*F&)%J *9.&I$H .&+,F*.2'% F MeOH.;#.3)22 /.&)%$& 1*)$#),.&$%% .&+,F*.& +*+,&F'2'& ~5–15 41//4'. 8*':0#))HJ .&+,F*."*5&F&'+2 F 1&"%''2. + "*4*M(T S".%$#F*/* )&+*+& KDScientific.
-&".2Y#)%#, +*I5&F*# )&1*)#0)*4 ^'#1,.*5#, % )&".2Y#)%# )& 1&"%''2.# +*+,&F'2'% d500 ; % d4500 ; (Z!>+-O!) %'%3500 ; (Z!>–-O!), +**,F#,+,F#))*, ".% "*,*1# .&+,F*.& *9.&I$& 0#.#I 1&"%''2. 3 41'/4%).-&".2Y#)%# )& FH3*5# 1&"%''2.& +*+,&F'2'* *, ±40 5* ±150 ;. O&++-+"#1,.H Z!>+ % Z!>–I&"%+HF&'% F 5%&"&I*)# m/z *, 50 5* 3000. =&F'#)%# *+:S&TM#/* /&I& F .&+"H'%,#'#+*+,&F'2'* 0.4 9&., +1*.*+,( "*,*1& % ,#4"#.&,:.& *+:S&TM#/* /&I& +*+,&F'2'% 4.0 '/4%) %180 °! +**,F#,+,F#))*.