Диссертация (1150306), страница 3
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\,&'*$%&)%)H %4#T, */.*4):T".*4HS'#)):T I)&0%4*+,( F+'#5+,F%# 9*'(S*/* 0%+'& +"*+*9*F %3 ".%4#)#)%2, F ,*4 0%+'# F+*F.#4#))H3 ,#3)*'*/%23 [23]. 6*'(S%)+,F* +"*+*9*F "*':0#)%2 K,&'*$%&)%)*F *+)*F&)* )&,#4"'&,)*4 +%),#I# F ".%+:,+,F%% 4#,&''*F % I&4#M#))H3 K,&'*5%)%,.%'*F. ; 9*'(S%)+,F#+':0&#F .#&1$%% ".*,#1&T, F YU+,1%3 :+'*F%23 (100–200 ºC) [23].
; ".%+:,+,F%% +*'#J )%1#'2% 1#,*1+%4& :5&U,+2 "*':0%,( K,&'*$%&)%)H F +:M#+,F#))* 9*'## 42/1%3 :+'*F%23 (65–100 ºC)[23] (8O9P< 11, c).!!13!aNONi2+4 Me2C=NOH2O[NiII]N4 H2ONNOO2+4 Me2C=NOHNi2+NH2CMe2CMe2NNNO ONibO ONNc–4 Me2C=NOH–2 NH34 H 2ONCMe2CMe2 H N2!O9P< 10. X%5.*'%I K,&'*)%,.%'& % %5#),%K%$%.*F&))HJ %),#.4#5%&,.R2+R1aNR1Ni2+4 Me2C=NOH2ORNR/R1 = H/HCl/ClNO2/HR1RRNNNcRNR1RNi2+2NCMe2CMe2 H N2R1R1ONNH2CMe2CMe2NNNO ONiNNR1NNiNbN2RNNN4 Me2C=NOHNR1RR1R!O9P< 11. 8.*4*,%.:#4HJ *1+%4&4% +%),#I K,&'*$%&)%)*F.7F,*.&4 .&9*,H [23] :5&'*+( FH5#'%,( %),#.4#5%&, 5&))*J .#&1$%%, ".#5+,&F'2TM%J+*9*J 1*4"'#1+ )%1#'2 + 5F:42 ,.%5#),&,)H4% '%/&)5&4%, "*':0#))H4% +*0#,&)%#4K,&'*5%)%,.%'& % 1#,*1+%4& F +**,)*S#)%% 1:2, &)&'*/%0)HJ *"%+&))*4: )& 8O9P9 10 (8O9P<11, a), 1*,*.HJ ".#,#."#F&#, ".#F.&M#)%# F* K,&'*$%&)%)*FHJ 1*4"'#1+ )%1#'2(II) F".%+:,+,F%% 5*"*')%,#'()H3 2 ^1F K,&'*5%)%,.%'& (8O9P< 11, b). >4 ,&1Y# :5&'*+(+%),#I%.*F&,( +F*9*5)H# K,&'*$%&)%)H F *,+:,+,F%# 4#,&''& %I K,&'*5%)%,.%'& ".%".*4*,%.*F&)%% .#&1$%% 1#,*1+%4&4% [23].!!14!1.4 (9<D=77 <HIGED87PEF 8 DEE:G7A7:EF<AABP7 A7;:7H<P7-#+4*,.2 )& ,*, 0,* *9H0)* &'(5*1+%4H % 1#,*1+%4H ".*2F'2T, +3*Y%# ):1'#*K%'()H#+F*J+,F&, 1*)#0)H4% ".*5:1,&4% 4#,&''*".*4*,%.:#4*/* +*0#,&)%2 &'(5*1+%4*F + )%,.%'&4%2F'2T,+2 )# 4-%4%)*&$%'&'(5*1+%4H.
6H'* *9)&.:Y#)* [13, 43-45, 60-63], 0,* *9.&I:TM%#+21**.5%)%.*F&))H# %4%)H RC(H)=NOC(=NH)R' (cO9P< 12, a) ".#,#."#F&T, .&+"&5 )& )%,.%'RCN % &4%5 R'CONH2 (cO9P< 12, b % c). ; I&F%+%4*+,% *, :+'*F%J ".*F#5#)%2 .#&1$%% :5&U,+2"*':0%,( 1&1 )%,.%' R'CN, ,&1 % +**,F#,+F:TM%J &4%5 R'CONH2 F .#I:'(,&,# "*+'#5:TM#J1&,&'%,%0#+1*J /%5.&,&$%% *9.&I:TM#/*+2 )%,.%'& (cO9P< 12, d).;"#.FH# 5&))HJ ".*$#++ :5&'*+( )&9'T5&,( :0U)H4 !89XP (cO9P< 13) [13]. 6H'**9)&.:Y#)*, 0,* ".*5:1,H ".%+*#5%)#)%2 &'(5*1+%4*F 1 ".*"%*)%,.%'()*4: 1*4"'#1+:"'&,%)H(IV) 1$",+-[PtCl4(EtCN)2] (cO9P< 13, A) )# :+,*J0%FH % 5&Y# F 42/1%3 :+'*F%23".#,#."#F&T, .&+"&5 )& )%,.%' (cO9P< 13, C) % 1&.9*1+&4%5)HJ 1*4"'#1+ "'&,%)H(IV) (cO9P<13, B).OHNRR'NHRHOR'cNR'[M]ROHHN[M]–[M]ONNbNHR'a[M]R[M]RR'NH2OOH2OdNH2NH2!O9P< 12. ;I&%4*5#J+,F%# &'(5*1+%4*F + )%,.%'()H4% 1*4"'#1+&4% % 5&'()#JS%J .&+"&5 4%4%)*&$%'&'(5*1+%4*F.D& "*+'#5)%# "2,( '#, 4#,&''*".*4*,%.:#4&2 5#/%5.&,&$%2 &'(5*1+%4*F F ".%+:,+,F%%)%,.%'*F "*':0%'& S%.*1*# .&+".*+,.&)#)%# % 9H'& .#&'%I*F&)& F 1&,&'%,%0#+1%3 F&.%&),&3+ %+"*'(I*F&)%#4 4#,&''*$#),.*F PdII [61, 62], RhI [44], InIII [43], CuII [45, 60], NiII [60], CoII [60],ZnII [60], FeII [60], MnII [60] % MoVI [63].
=&))H# .#&1$%% )&S'% ".%4#)#)%# F 5F:3)&".&F'#)%23: "*':0#)%# 1&.9*1+&4%5*F R'CONH2 %I &'(5*1+%4*F R'C(H)NOH (!O9P< 12, a–d)% +%),#I 1&.9*1+&4%5*F RCONH2 %I )%,.%'*F RCN (!O9P< 12, a–c).!!15!OHNNR'H[PtIV]MeR' = Me; Ph; PhCOHOR'NMeHN[PtIV]NR'HBCOMeHN[PtIV]A!O9P< 13. ;I&%4*5#J+,F%# &'(5*1+%4*F + ".*"%*)%,.%'()H4 1*4"'#1+*4 "'&,%)H(IV) %.&+"&5 *9.&I:TM#/*+2 %4%)&.C&,&'%I%.:#4HJ4#,&''&4%".*$#++5#/%5.&,&$%%&'(5*1+%4*FR'C(H)NOH+"*':0#)%#4 )%,.%'*F R'CN :5&'*+( .#&'%I*F&,( 9#I :0&+,%2 )%,.%'& RCN 1&1 F /*4*/#))*4F&.%&),# ".% 1&,&'%I# 1*4"'#1+&4% Re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l)=NOH [27] % &4%5*1+%4H RC(NH2)=NOH [30, 47, 48].!*0#,&)%# 4#,*1+%*1+%4*F % 3'*.1+%4*F + )%,.%'()H4% 1*4"'#1+&4% "'&,%)H(IV)".%F*5%, 1 *9.&I*F&)%T 1*4"'#1+*F + 5F:42 4*)*5#),&,)* 1**.5%)%.*F&))H4% 4%4%)*&$%'*1+%4&4% (8O9P< 14).
G#&1$%% + 4#,*1+%*1+%4&4% ".*,#1&T, I& 15 4%) ".% 20–45 ºC[66], + 3'*.1+%4&4% I& 9*'## 5'%,#'()*# F.#42 (38–240 0) ".% 45 ºC [27].G#&1$%%+*0#,&)%2&4%5*1+%4*F+)%,.%'&4%%IF#+,)H1&15'2%)#.,)*/*4#,&''*$#),.& – "'&,%)H(IV) [27], ,&1 % '&9%'()*/* – $%)1&(II) [30, 47, 48]. B&1Y# %IF#+,)&"*5*9)&2 .#&1$%2 F 9#I4#,&''()*4 F&.%&),# + "#.K,*.%.*F&))H4% &'%K&,%0#+1%4% )%,.%'&4%,.#0( * 1*,*.H3 "*J5U, )%Y# [55]. <5%)+,F#))H4 ".%4#.*4 +*0#,&)%2 &4%5*1+%4& + )%,.%'*4,1**.5%)%.*F&))H4 1 "'&,%)#(IV), 9H'& /#,#.*/#))&2 .#&1$%2 4#Y5: &$#,*)%,.%'()H41*4"'#1+*4 1$",+-[PtCl4(MeCN)2] % 9#)I&4%5*1+%4*4 PhC(NH2)=NOH ".% 56 ºC F ,#0#)%#27 0, 1*,*.&2 ".%F*5%'& 1 %4%)*1*4"'#1+: "'&,%)H(IV), +*5#.Y&M#4: 5F& 4*)*5#),&,)*1**.5%)%.*F&))H3 4-%4%)*&$%'&4%5*1+%4)H3 '%/&)5& (8O9P< 15) [27]. ;I&%4*5#J+,F%#!16!!&4%5*1+%4*F + )%,.%'&4% %),#.#+)* ,#4, 0,* ".%F*5%, 1 3,5-5%I&4#M#))H4 1,2,4*1+&5%&I*'&4 [30, 47, 48, 67].ClRN PtClClR1ClNNX2RR2R1X = OMeR = Me, EtR1/R2 = H/HMe/MeCH2Cl2R2OHX = ClR = MeR1/R2 = H/HH/MeH/NO2R1RR1NXClHN PtClClROClNOXNHR1R1R2!O9P< 14.
!*0#,&)%# K:)1$%*)&'%I%.*F&))H3 *1+%4*F + )%,.%'()H4% 1*4"'#1+&4%"'&,%)H(IV).ClMeClPt NNClN2MePhClOHNH256 ºC; 27 hPhHMeNNHOHCl ClN PtCl ClMeONHNHNHPh!O9P< 15. >IF#+,)HJ ".%4#. +*0#,&)%2 &4%5*1+%4& + )%,.%'()H4 1*4"'#1+*4 "'&,%)H(IV).!!17!1.6 !7A;9R 1,2,4-ED8<G7<REHEF 7R <P7GED87PEF8.*%IF*5)H# 1,2,4-*1+&5%&I*'*F ".#5+,&F'2T, +*9*J I)&0%4HJ 1'&++ "2,%0'#))H3/#,#.*$%1'*F, %3 .&I)*+,*.*))## ".%4#)#)%# F 3%4%% *,.&Y#)* F *9I*.&3 [68-71].;*I.&+,&TM## 1*'%0#+,F* ":9'%1&$%J, 1&+&TM%3+2 5&))H3 +*#5%)#)%J, +F2I&)* + F&Y)*+,(T1,2,4-*1+&5%&I*'*F 1&1 F 3%4%% 4&,#.%&'*F (F3*52, F +*+,&F "*'%4#.*F [68], Y%51%31.%+,&''*F % %*))H3 Y%51*+,#J [68, 72-74], 'T4%)#+$#),)H3 [68, 72] % *",*^'#1,.*))H34&,#.%&'*F [68], & ,&1Y# %)/%9%,*.*F 1*..*I%%) [75], ,&1 % F K&.4&1*'*/%% [68, 76](%+"*'(I:T,+2 F 1&0#+,F# ".*,%F*5%&9#,%0#+1%3 [68], ".*,%F*F*+"&'%,#'()H3 [68, 77],".*,%F*4%1.*9)H3 [68, 73, 78, 79] % ".*,%F*.&1*FH3 ".#"&.&,*F [68, 76, 80, 81], & ,&1Y# F1&0#+,F# %44:)*+:".#++*.*F [68, 73], K:)/%$%5*F % '&.F%$%5*F [82]).
!.#5% F+#3 %IF#+,)H3+"*+*9*F "*':0#)%2 1,2,4-*1+&5%&I*'*F 4*Y)* FH5#'%,( 5F& *+)*F)H3 )&".&F'#)%2: 1,35%"*'2.)*# $%1'*".%+*#5%)#)%# )%,.%'*1+%5*F 1 )%,.%'&4 (8O9P< 16, ") % FI&%4*5#J+,F%#&4%5*1+%4*F + &1,%F%.*F&))H4% 1&.9*)*FH4% 1%+'*,&4% % 4)*/%4% %3 ".*%IF*5)H4% (8O9P<16, !), F ,*4 0%+'# + )%,.%'&4% (8O9P< 16, d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–180 º!) [86].
P+'*F%2 .#&1$%% 4*/:, 9H,( +:M#+,F#))*+42/0#)H (5* 20–80 ºC), #+'% ".*F*5%,( #U F ".%+:,+,F%% 3'*.%5& $%)1& % +%'()*J 1%+'*,H[HCl %'% #-,*':*'+:'(K*1%+'*,H (8B!C)] [30, 47, 48]. 8*4%4* ^,*/*, %IF#+,#) ".%4#.&1,%F&$%% )%,.%'*F ":,U4 "*':0#)%2 %I )%3 )%,.%'%#FH3 +*'#J [67]. ; ^,*4 +':0&#, .#&1$%2".*,#1&#, + *9.&I*F&)%#4 1,2,4-*1+&5%&I*'*F, % ".*4#Y:,*0)H# )#+,&9%'()H# %4%)%#FH# +*'%:5&'*+( 5#,#1,%.*F&,(.7F,*.H .&9*,H [47] ".%4#)%'% +%+,#4: ZnCl2 + 8B!C 5'2 :+1*.#)%2 +*0#,&)%2&4%5*1+%4*F + )%,.%'&4% % ".#5"*'*Y%'%, 0,* ZnII +"*+*9+,F:#, *,M#"'#)%T &44%&1& *,&4%5*1+%4&, *9.&I:#,+2 )%,.%'*1+%5, 1*,*.HJ I&,#4 .#&/%.:#, + )%,.%'*4 1&1 1,3-5%"*'((8O9P< 17, ").RZnII/PTSAR'– NH3NNOR'ZnIIaRNNH2N[Zn]ObHCl–ZnCl2;NH4ClNHR'RR'NNONH2HOR'RNcRNR"NH2ONHdRN–[NH3R"]+R"R'NRNR = perfluorinatedalkylONH2NHCF3COF–HF; CF3CONH2R!O9P< 17. G&)## ".#5"*'&/H# 4#3&)%I4H *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F %I )%,.%'*F %&4%5*1+%4*F.7F,*.H .&9*,H [30] %I:0%'% +3*Y:T 1&,&'%,%0#+1:T +%+,#4: (ZnCl2 + HCl) + "*4*M(T+"#1,.*+1*"%% AOG 15N %, )#+4*,.2 )& ,*, 0,* )% *5%) %I %),#.4#5%&,*F )# 9H' FH5#'#) F!19!!0%+,*4 F%5#, ".#5'*Y%'% %)*J 4#3&)%I4 *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F.
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