Диссертация (1150306), страница 6
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;H9.&))H# *9_#1,H %++'#5*F&)%2.; *,'%0%# *, "'&,%)H(IV) "'&,%)&(II) +:M#+,F#))* +'&9## &1,%F%.:#, )%,.%'H "**,)*S#)%T 1 ):1'#*K%'()*4: ".%+*#5%)#)%T [53], % )& 5&))*4 4#,&''*$#),.# :5&U,+2I&K%1+%.*F&,( .&I)%$: F .#&1$%*))*J +"*+*9)*+,% )%,.%'*F. -&".&F'#)%# .#&1$%% 4#Y5:1*4"'#1+&4% 26–31 % &4%5*1+%4&4% 4, 6 F I)&0%,#'()*J +,#"#)% I&F%+%, *, 1$",+/5*+1*)K%/:.&$%% %+3*5)*/* 1*4"'#1+& % ".%.*5H I&4#+,%,#'2 F )%,.%'#.(9<D=77 8 1 ]DF <P7GED87P<. !*#5%)#)%2 26–29, +*5#.Y&M%# 1**.5%)%.*F&))H#):;.,;- )%,.%'H, .#&/%.:T, + 1 ^1F &4%5*1+%4*F 4, 6 (F* F+#3 F*I4*Y)H3 1*49%)&$%23) +*9.&I*F&)%#4 1*4"'#1+*F 36–43 + 4*)*5#),&,)* 1**.5%)%.*F&))H4 %4%)*'%/&)5*4 +".#"&.&,%F)H4% FH3*5&4% 55–92% (8O9P< 21, b; 8O9P< 22, b).
; +F*T *0#.#5(,5%&'1%'$%&)&4%5)H# 1*4"'#1+H 30 % 31 .#&/%.:T, + 1 ^1F &4%5*1+%4*F 4 % 6 + *9.&I*F&)%#41&,%*))H3 (32[Cl] % 33[Cl]) % )#J,.&'()H3 (34 % 35) 3#'&,)H3 1*4"'#1+*F +**,F#,+,F#))*(8O9P< 21, a; 8O9P< 22, a).!!36!(X)2HR'ClHR'RNR'HNNPtNHClNH2NeNRR = NMe2R'RNH2NcPtb4, 6R = NMe2ClaN2RClR = Et, PhRNPtNNOClR'2 AgNO3,–2 AgClNH24, 6R = Et, Ph26, 28, 30NNOHdR'HRH[44](Cl)2, [45](Cl)2,[46](NO3)2–[48](NO3)2NOHClONHH[32](Cl), [33](Cl)R'NPtO4, 6OHHNRNOHNRHR = PhfHHNR'RNH2NHPtHNNNOClR'4, 636–39ONNOHHR'ClHgHR55–57!O9P< 21. !%),#,%0#+1%# ".#F.&M#)%2 1$",+-1*4"'#1+*F 26, 28, 30.HHClClNHPtNR'NNO! –NCNMe2NH2ClaR = Et, PhNNRRONeRR'HClHClRPtNNH24, 62 AgNO3,–2 AgClNH24, 6NOHR'R'R = Et, PhR = PhHNOHdRN40–432RNHNHc27, 29, 31ClPtNNHR = NMe2ClPtb4, 6ClO[49](Cl)2, [50](Cl)2,[51](NO3)2–[54](NO3)2R = NMe2NOHHNPtR34, 35RNORR'NHH(X)2HR'R'ONHNHONNNHfHR'R'58–61!O9P< 22.
!%),#,%0#+1%# ".#F.&M#)%2 5*+-1*4"'#1+*F 27, 29, 31.H!!37!(9<D=77 8 2 ]DF <P7GED87P<. C*4"'#1+H [32](Cl), [33](Cl) % 38–43, "*':0#))H# ":,U44*)*+*0#,&)%2, 9H'% ".#F.&M#)H F +**,F#,+,F:TM%# ".*5:1,H 9%++*0#,&)%2 [44](Cl)2,[45](Cl)2 (8O9P< 21, e) % 56–61 (8O9P< 21, f; 8O9P< 22, e) ":,U4 .#&1$%% + 1 ^1F+**,F#,+,F:TM#/* &4%5*1+%4&. 7'(,#.)&,%F)* ".*5:1,H 9%++*0#,&)%2 [44](Cl)2, [45](Cl)2, 56 %57 (8O9P< 21, ! % d), [49](Cl)2 % [50](Cl)2 % 58–61 (8O9P< 22, ! % d) 9H'% "*':0#)H .#&1$%#J%+3*5)H3 )%,.%'()H3 1*4"'#1+*F 26–31 + 2 ^1F &4%5*1+%4*F 4 % 6 F .&+,F*.# MeNO2 I& 10–100 0 ".% 1*4)&,)*J ,#4"#.&,:.# + ".#"&.&,%F)H4% FH3*5&4% 62–87%.-&".&F'#)%# .#&1$%% ".*"%*)%,.%'()H3 1*4"'#1+*F 26 % 27 + &4%5*1+%4&4% 4 % 6I&F%+%,*,1$",+/5*+-1*)K%/:.&$%%%+3*5)H31*4"'#1+*F.G#&1$%24#Y5:1$",+-".*"%*)%,.%'()H4 1*4"'#1+*4 26 + 2 ^1F &4%5*1+%4*F 4 % 6 F )%,.*4#,&)# ".% 1*4)&,)*J,#4"#.&,:.# ".*,#1&#, F ,#0#)%# 2 +:, % ".%F*5%, 1 *9.&I*F&)%T +4#+% 9*'(S*/* 1*'%0#+,F&)#%5#),%K%$%.*F&))H3 ".*5:1,*F.
-#+4*,.2 )& ^,*, )&4 :5&'*+( FH5#'%,( 1.%+,&''H".*5:1,& 9%++*0#,&)%2 1$",+-[PtCl2{HN=C(Et)ON=C(NH2)Ph}2]•2MeOH 55 ":,U4 .#&1$%%1$",+-[PtCl2(EtCN){HN=C(Et)ON=C(NH2)Ph}] 37 + 1 ^1F 9#)I&4%5*1+%4& 6 I& 2 +:, F 4#,&)*'#".% 1*4)&,)*J ,#4"#.&,:.# + ".#"&.&,%F)H4 FH3*5*4 33% (*+,&'()H# ".*5:1,H .#&1$%%*+,&T,+2 F .&+,F*.#). 7)&'*/%0)&2 .#&1$%2 + &$#,&4%5*1+%4*4 4 F ,&1%3 Y# :+'*F%23 ".%F*5%,1 *9.&I*F&)%T +4#+% ".*5:1,*F, *+&5*1 )# FH"&5&#,.<*+-".*"%*)%,.%'()HJ 1*4"'#1+ 27 .#&/%.:#, + 2 ^1F &4%5*1+%4*F 4 % 6 F ,#0#)%# 2 +:,F MeNO2 ".% 1*4)&,)*J ,#4"#.&,:.# + *9.&I*F&)%#4 ".*5:1,*F 9%++*0#,&)%2 58, 59 +3*.*S%4% FH3*5&4% (66 % 69% +**,F#,+,F#))*) (8O9P< 22, d).6#)I*)%,.%'()H# 1*4"'#1+H 28 % 29 F+,:"&T, F .#&1$%T + 2 ^1F &4%5*1+%4*F 4 % 6 F,#0#)%# 1 +:, F MeNO2 ".% 1*4)&,)*J ,#4"#.&,:.# + *9.&I*F&)%#4 ".*5:1,*F 9%++*0#,&)%2 56,57 % 60, 61 (8O9P< 21, d; 8O9P< 22, $ +**,F#,+,F#))*).=%4#,%'$%&)&4%5)H# 1*4"'#1+H 30 % 31 .#&/%.:T, + 2 ^1F &4%5*1+%4*F 4 % 6 +*9.&I*F&)%#4 %I*4#.)H3 9%+3#'&,)H3 1*4"'#1+*F [44](Cl)2, [45](Cl)2, [49](Cl)2 % [50](Cl)2(8O9P< 21, !; 8O9P< 22, !).
1$",+-C*4"'#1+ 30 *9.&I:#, 1*4"'#1+H [44](Cl)2 % [45](Cl)2 I& 10 0 FMeNO2 ".% 1*4)&,)*J ,#4"#.&,:.# + ".#"&.&,%F)H4% FH3*5&4% 73 % 82% +**,F#,+,F#))*.!**,F#,+,F:TM%# ".*5:1,H 4*)*+*0#,&)%2 [32](Cl) % [33](Cl) *9.&I*FHF&'%+( I& 10 4%).G#&1$%2 5*+-1*4"'#1+& 31 + &4%5*1+%4&4% F ,&1%3 Y# :+'*F%23 ".%F*5%, 1 +4#+% 9*'(S*/*1*'%0#+,F& )#%5#),%K%$%.*F&))H3 ".*5:1,*F. 6%+3#'&,)H# 1*4"'#1+H [49](Cl)2 % [50](Cl)29H'% "*':0#)H 9*'## +#'#1,%F)* + ".#"&.&,%F)H4% FH3*5&4% 62 % 75% +**,F#,+,F#))* ".%–8 ºC I& 100 0 F MeNO2.!!38!3.3 L9H<;7:EF<A79 #-7P7AE<=7H<P7GED87PEF R< 8@^; Q:7A?G7;9HIAEC G9DEE:G7A<=77OHE:7G-<A7EA<-&4% 9H'* *9)&.:Y#)*, 0,* ".*5:1,H 9%++*0#,&)%2 56–61 ".*"%*)%,.%'()H3 %9#)I*)%,.%'()H3 1*4"'#1+*F 26–29 )# ".#,#."#F&T, ".#F.&M#)%2 F +**,F#,+,F:TM%#9%+3#'&,)H# 1*4"'#1+H [47](Cl)2, [48](Cl)2 % [51](Cl)2–[54](Cl)2 F .&+,F*.# MeNO2 5&Y# ".%100 ºC % F ,FU.5*J K&I# ".% ,#4"#.&,:.&3 )& 5 ºC )%Y# ,#4"#.&,:.
.&I'*Y#)%2 5&))H31*4"'#1+*F. B#4 )# 4#)## 9%+3#'&,)H# 1*4"'#1+H [47](NO3)2 % [48](NO3)2 % [51](NO3)2–[54](NO3)2 9H'% "*':0#)H .#&1$%24% 56, 57 (8O9P< 21, g) % 58–61 (8O9P< 22, f), +**,F#,+,F#))*,+ 2 ^1F AgNO3.8*5*9)H4 *9.&I*4 9H' "*':0#) 9%+3#'&,)HJ 1*4"'#1+ [46](NO3)2 %I 1*4"'#1+& 55 +1*'%0#+,F#))H4 FH3*5*4. 8.%4#)#)%# ,.%K'&,& +#.#9.& CF3SO3Ag (TfOAg) F 5&))*J .#&1$%%)# .#1*4#)5:#,+2 F+'#5+,F%# ,*/*, 0,* FH5#'#)%# 1*)#0)*/* ".*5:1,& %I .#&1$%*))*J +4#+%+%'()* I&,.:5)#)* %I-I& 9'%I1*J .&+,F*.%4*+,% 1*4"'#1+& [46](OTf)2 % "*9*0)H3 ".*5:1,*F.-#+4*,.2 )& ^,*, %+"*'(I:2 ,.%K'&, +#.#9.& F 5&))*J .#&1$%%, )&4 :5&'*+( "*':0%,(1.%+,&''H1*4"'#1+& [46](OTf)2, ".%/*5)H# 5'2 G!7, "*5,F#.5%FS#/* ".#5"*'&/:T+,.:1,:.: 9%+3#'&,)*/* 1&,%*)&. G#&1$%2 1*4"'#1+& 26 + &4%5*1+%4*4 4 )# ".%F*5%, 1*9.&I*F&)%T 9%+3#'&,)*/* 1*4"'#1+& F .&+,F*.&3 MeOH, EtOH % MeNO2 ".% %+"*'(I*F&)%%1&1 )%,.%,& +#.#9.&, ,&1 % ,.%K'&,& +#.#9.& F ,#4"#.&,:.)*4 5%&"&I*)# *, –8 5* +50 ºC.3.4 (<RH7@79 :9<D=7EAAEC 8QE8EZAE8;7 <P7GED87PEF 7 D9;ED87PEF; .&41&3 5&))*J 0&+,% .&9*,H 4H *9)&.:Y%'%, 0,* ):1'#*K%'()*# ".%+*#5%)#)%#&4%5*1+%4*F 4 % 6 1 )%,.%'&4, 1**.5%)%.*F&))H4 1 "'&,%)#(II), ".*,#1&#, 9#I 5*"*')%,#'()*JF)#S)#J &1,%F&$%% )# ,*'(1* ".% 1*4)&,)*J ,#4"#.&,:.#, )* 5&Y# ".% –8 ºC (5'2 [49](Cl)2 %[50](Cl)2) + *9.&I*F&)%#4 %4%)*&$%'%.*F&))H3 ".*5:1,*F + 3*.*S%4% FH3*5&4%.Z,% )&9'T5#)%2 "*51.#"'2T,+2 )&S%4% ^1+"#.%4#),&'()H4% 5&))H4% "* *$#)1#+.&F)%,#'()*J .#&1$%*))*J +"*+*9)*+,% &4%5*1+%4*F % 1#,*1+%4*F.
-&4% 9H' ".*F#5U)AOG-4*)%,*.%)/ .#&1$%J 1$",+-".*"%*)%,.%'()*/* 1*4"'#1+& 26 + 9#)I&4%5*1+%4*4 6 %&$#,*K#)*)*1+%4*4 PhC(=NOH)Me F CDCl3 (8O9P< 23). C*4"'#1+ 26 )&4% 9H' FH9.&) 5'2%++'#5*F&)%2 F+'#5+,F%# ,*/*, 0,* +.#5% F+#3 %I:0H3 F 5&))*J /'&F# "'&,%)*FH3+*#5%)#)%J F )U4 ".%+*#5%)#)%# "* F,*.*4: )%,.%'()*4: '%/&)5: ".*,#1&#, 4#5'#))## F+#/*,% .#&1$%2 4*Y#, 9H,( *+:M#+,F'#)& +#'#1,%F)* 1&1 4*)*+*0#,&)%#.!!39!ClEtNPtNOHNEtPhClRR = Me, NH2CDCl3; 23 ºCPhClEtNPtHNClNOREt!O9P< 23. >++'#5*F&)%# +1*.*+,% .#&1$%J +*0#,&)%2 *1+%4*F + 1*4"'#1+*4 26.; .#I:'(,&,# ^1+"#.%4#),& (+ 5*":M#)%#4 ,*/*, 0,* +*0#,&)%# *1+%4& +* F,*.H4^1F%F&'#),*4 )%,.%'& )# ".*%+3*5%,, % "*9*0)H# .#&1$%% *,+:,+,F:T,) )&4% 9H'% FH0%+'#)H1*)+,&),H +1*.*+,% *9#%3 .#&1$%J (+4. ^1+"#.%4#),&'():T 0&+,(, +. 83). G&+0U,H "*1&I&'%, 0,*1*)+,&),& +1*.*+,% .#&1$%% + 1#,*1+%4*4 .&F)& (2.57±0.10)•10–3 O–1•c–1, & .#&1$%% +&4%5*1+%4*4 – (6.70±0.33)•10–2 O–1•c–1 (".% 23 ºC).
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l), [33](Cl), 34, 35, [44](Cl)2, [45](Cl)2, [49](Cl)2 %[50](Cl)2, F ,* F.#42 1&1 1*4"'#1+H ):;.,;& )%,.%'*F 26–29 .#&/%.:T, + &4%5*1+%4&4% 4 % 6 +*9.&I*F&)%#4 4*)*5#),&,)* 1**.5%)%.*F&))H3 %4%)*F 36–43 % 55–61. =&))*# )&9'T5#)%#4*Y)* *9_2+)%,(, + *5)*J +,*.*)H, 4#)(S#J ^)#./%#J &1,%F&$%% %)F#.+%% +F2I% C=N F5%&'1%'$%&)&4%5)H3 ".*%IF*5)H3 F+'#5+,F%# +*".2Y#)%2 + /.:""*J NMe2, & + 5.:/*J+,*.*)H, +,#.%0#+1%4 )&".2Y#)%#4 F K.&/4#),# 5*+-{Me2N–C=N–PtCl4}.
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