Диссертация (1150306), страница 2
Текст из файла (страница 2)
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«".*+,H#» *1+%4H [13-15, 17-23], 1,2-5%*1+%4H [24] %K:)1$%*)&'%I%.*F&))H# *1+%4H [25-30], ".%F*52, 1 *9.&I*F&)%T +F2I% C–O{N}, F .#I:'(,&,#&,&1% HO /.:""H "* +F2I% C`N (8O9P< 2).HO[M]NRR'HN[M]R''NNOR''R'R!O9P< 2.
!*0#,&)%# *1+%4*F + )%,.%'()H4% '%/&)5&4% F 1*4"'#1+&3 4#,&''*F, ".%F*52M## 11**.5%)%.*F&))H4 4-%4%)*&$%'*1+%4&4.6*'## ,*/*, ".*F*5%4H# F ".%+:,+,F%% '&9%'()H3 4#,&''*$#),.*F (CoII [31], NiII [22, 23,32-37] % ZnII [38]), 5&))H# .#&1$%% %4#T, 9*'(S*# ".%1'&5)*# I)&0#)%#, ,&1 1&1 ".%F*52, 1I)&0%4H4 1'&++&4 *./&)%0#+1%3 +*#5%)#)%J, ,&1%3 1&1 &4%5%)H [31], &$%'&4%5H [32], 1,3,5,.%&I&"#),&5%#)H [32-36, 39, 40], 1&.9*1+&4%5H [38, 41-45], K,&'*$%&)%)H [23, 46] % 1,2,4*1+&5%&I*'H [30, 47, 48].!!7!1.2 (9<D=77 D9;ED87PEF 8 DEE:G7A7:EF<AABP7 A7;:7H<P7R&.&1,#. *9.&I:TM%3+2 ".*5:1,*F % +"*+*9 ".*F#5#)%2 .#&1$%% +*0#,&)%2 *1+%4*F +)%,.%'()H4% 1*4"'#1+&4% I&F%+%, *, ".%.*5H 4#,&''*$#),.&.
<+'% F 1&0#+,F# &1,%F&,*.&%+"*'(I:#,+2 %)#.,)HJ 4#,&''*$#),., )&".%4#., "'&,%)&(IV) [16, 21, 24] %'% .#)%J(IV) [49],*9.&I:T,+2 1*4"'#1+H + 4*)*5#),&,)* 1**.5%)%.*F&))H4 4-%4%)*&$%'*1+%4*4, 1*,*.HJ%4##, 8-1*)K%/:.&$%T 1**.5%)%.*F&))*J %4%)*/.:""H + F):,.%4*'#1:'2.)*J F*5*.*5)*J+F2I(T 4#Y5: &,*4*4 F*5*.*5& %4%)*/.:""H % *1+%4)H4 &,*4*4 &I*,& (8O9P< 3). G#&1$%%*1+%4*F + 1*4"'#1+&4% 1$",+-[PtCl4(RCN)2] (R = Me, Et, Ph), [PtCl5(EtCN)] % 5*+[ReCl4(MeCN)2] ".*,#1&T, F 42/1%3 :+'*F%23 "*0,% + 1*'%0#+,F#))H4% FH3*5&4%. 7F,*.&4%.&9*, [16, 21, 24, 49] 9H'* ,&1Y# "*1&I&)*, 0,* *1+%4H )# .#&/%.:T, +* +F*9*5)H4% )%,.%'&4%,0,* +F%5#,#'(+,F:#, * )#*93*5%4*+,% &1,%F&$%% )%,.%'&.HO[M]NRR'M=PtIV,R''HN[M]NOR''ReIVNR'R!O9P< 3.
!*0#,&)%# *1+%4*F + )%,.%'()H4% 1*4"'#1+&4% "'&,%)H(IV) % .#)%2(IV).8.% %+"*'(I*F&)%% *,)*+%,#'()* '&9%'()H3 4#,&''*$#),.*F, ,&1%3 1&1 F&)&5%J(IV) [50,51], .*5%J(III) [17, 18], )%1#'((II) [37, 52] %'% "&''&5%J(II) [20] .#&1$%2 ".*,#1, +*9.&I*F&)%#4 3#'&,)H3 1*4"'#1+*F, F 1*,*.H3 4-%4%)*&$%'*1+%4 1**.5%)%.*F&) 1 4#,&'':5F:42 &,*4&4% &I*,&. ; 5&))*4 +':0 .#&1$%T F*I4*Y)* .#&'%I*F&,( 5F:42 +"*+*9&4%:%+3*52 %I *1+%4& % )%,.%'()*/* 1*4"'#1+& 4#,&''& %'% %I )%,.%'& % *1+%4)*/* 1*4"'#1+&.?9& F&.%&),& ".%F*52, 1 *5)*4: % ,*4: Y# ".*5:1,: (8O9P< 4). 8.#5"*'&/,+2, 0,* +)&0&'&".*%+3*5%, *9.&I*F&)%# 1*4"'#1+& 4#,&''&, +*5#.Y&M#/* )%,.%' % *1+%4 F 5*+-"*'*Y#)%%5.:/ 1 5.:/:, I&,#4 – F):,.%+K#.)*# +*0#,&)%# ".*+,.&)+,F#))* +9'%Y#))H3 *1+%4& %)%,.%'&; "*+'#5)%J &1,%F%.:#,+2 I& +0U, 1**.5%)&$%%.B&1%4 *9.&I*4, *, ".%.*5H 4#,&''*$#),.& I&F%+%, +"*+*9 1**.5%)&$%% *9.&I:TM#/*+24-%4%)*&$%'*1+%4& % F*I4*Y)*+,( F+,.#0)*/* +%),#I& %I )%,.%'*F % *1+%4)H3 1*4"'#1+*F4#,&''*F.=.:/%4 F&Y)H4 K&1,*.*4, F'%2TM%4 )& ".*,#1&)%# .#&1$%%, 2F'2#,+2 +,#"#)(*1%+'#)%2 4#,&''*$#),.&.
;&Y)*+,( 5&))*/* K&1,*.& )&/'25)* ".*2F'2#,+2 F +.&F)#)%%.#&1$%J +*0#,&)%2 *1+%4*F + )%,.%'&4% )& "'&,%)#(IV) [16, 24, 25] % "'&,%)#(II) [14, 15, 19].?1+%4H '#/1* .#&/%.:T, + )%,.%'()H4% 1*4"'#1+&4% "'&,%)H(IV), 5&F&2 ".*5:1,H .#&1$%% +!8!!"*0,% 1*'%0#+,F#))H4% FH3*5&4% 5&Y# ".% 1*4)&,)*J ,#4"#.&,:.#, F ,* F.#42 1&1 )&"'&,%)#(II) ".*,#1&)%# "*5*9)H3 .#&1$%J I&,.:5)#)* 5&Y# F 9*'## YU+,1%3 :+'*F%23.N[M]NOHRR''RR'HNN[M]M = VIV, RhIII, NiII, PdIIR[M]OHNR''OHN[M]NR''R'NROR'R'R''!O9P< 4.
!*0#,&)%# *1+%4*F + )%,.%'&4% F ".%+:,+,F%% F&)&5%2(IV), .*5%2(III), )%1#'2(II) %"&''&5%2(II).; .&9*,# [19] "*1&I&)*, 0,* &1,%F&$%2 &'%K&,%0#+1%3 % &.*4&,%0#+1%3 )%,.%'*F"'&,%)*J(II) )#5*+,&,*0)& 5'2 :+"#S)*/* ):1'#*K%'()*/* ".%+*#5%)#)%2 1#,*1+%4*FR'2C=NOH (R'2 = Me2, C4H8) 1 )%,.%'()H4 '%/&)5&4. N%S( ".% %+"*'(I*F&)%%5%&'1%'$%&)&4%5)H3 1*4"'#1+*F 5*+-[Pt(NCNR2)2(PPh3)2]2+ (R = Me, Et) 9H'% "*':0#)H3#'&,)H# ".*5:1,H 4*)*+*0#,&)%2, ".%0U4 5'2 ".*,#1&)%2 .#&1$%% 9H'& )#*93*5%4&5*"*')%,#'()&2 ^'#1,.*K%'()&2 &1,%F&$%2 5%&'1%'$%&)&4%5& 1&,%*)&4% Ag+ %'% Cu2+,1*,*.H#, "* ".#5"*'*Y#)%T &F,*.*F, +F2IHF&T,+2 + /.:""*J NR2 (8O9P< 5) [19].NR2Ph3PR'R'Ag+ or Cu2+NHNPh3PPtPtPh3PNOH(BF4)2NNNR2NR2Ph3PR'NNR2(BF4)2OR'!O9P< 5. C&,&'%I%.:#4*# 1%+'*,&4% N(T%+& +*0#,&)%# 1#,*1+%4*F + )%,.%'()H4%1*4"'#1+&4% "'&,%)H(II).8*I5)## +*0#,&)%# *1+%4*F + )%,.%'()H4% '%/&)5&4% 9H'* .&+".*+,.&)#)* )& )%,.%'HRCN (R – ^'#1,.*)*&1$#",*.)H# /.:""H Ph, CH2Cl % CH2CO2Me).
G#&1$%2 ".*,#1&'& ".% 40–!9!!50 ºC %/%'% 4%1.*F*')*F*4 *9':0#)%% + *9.&I*F&)%#4 4*)*5#),&,)* 1**.5%)%.*F&))H3 4%4%)*&$%'*1+%4*F + :4#.#))H4% FH3*5&4% (8O9P< 6) [14, 15].ClRNPtNRCl50 ºC and/orMW irradiationR'R'NOH2R'R'RRNClHONPtClRNClONHR'ONR'NHNHPtClNR'ROR'R'R'!O9P< 6. >)5:$%.*F&))*# 4%1.*F*')*FH4 %I':0#)%#4 +*0#,&)%# 1#,*1+%4*F + )%,.%'()H4%'%/&)5&4% F 1*4"'#1+&3 "'&,%)H(II).G#I:'(,&,H ^1+"#.%4#),*F % ,#*.#,%0#+1%3 .&+0U,*F "*IF*'%'% :+,&)*F%,( *+)*F)H#5F%Y:M%# +%'H .&++4&,.%F*J .#&1$%% +*0#,&)%2 [21, 53, 54].
! *5)*J +,*.*)H,".#F.&M#)%# :+1*.2#,+2 I& +0U, ^'#1,.*K%'()*J &1,%F&$%% )%,.%'&, )&".%4#., 4#,&''&4% FFH+*1%3 +,#"#)23 *1%+'#)%2 (PtIV [16, 25, 27], ReIV [16, 25, 27, 49] % RhIII [17, 18]) %'% 4*M)H4%^'#1,.*)*&1$#",*.)H4% I&4#+,%,#'24%, ,&1%4% 1&1 "#.K,*.%.*F&))H# &'1%'H [55]. ! 5.:/*J+,*.*)H,".%)$%"%&'()*%)H4+"*+*9*4:+1*.#)%2+*0#,&)%22F'2#,+2:F#'%0#)%#):1'#*K%'()*+,% *1+%4&.
B#4 )# 4#)## %+"*'(I*F&)%# *1+%4*F + 9ó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
C*4"'#1+H&4%5%)*F ".%4#)2T,+2 F* 4)*/%3 ".*4HS'#))H3 ".*$#++&3 [58], & ,&1Y# F 1&0#+,F#".*,%F*.&1*FH3 ".#"&.&,*F [6]. 8.24*J +%),#I &4%5%)*F %I )%,.%'*F % &4%)*F F *,)*+%,#'()*42/1%3 :+'*F%23 F*I4*Y#) '%S( 5'2 */.&)%0#))*/* 0%+'& )%,.%'*F, +*5#.Y&M%3 4*M)H#&1$#",*.)H# /.:""H. <+'% )%,.%' +*5#.Y%, 5*)*.)H# I&4#+,%,#'%, ,* ".24*J +%),#I&4%5%)*F %I )%,.%'*F % &4%)*F )#F*I4*Y#) [31].aR–NH2 NO3Co(NO3)2R'2C=NOHNRR'2 = Me2, C4H8R = Me, Et, nPr, nBuNH2[CoII]bdR[CoII]NH+NO3–NH3–RCOOH–[CoII]c–[CoII]fR'2C=NOHR'eHNR'2H2ON[CoII]HNH3N–R'2C=NOHO[CoII]H2NRR!O9P< 7. !%),#I &4%5%)*F, ".*4*,%.:#4HJ 1#,*1+%4&4% % )%,.&,*4 1*9&'(,&(II).C**9M&'*+( [31], 0,* )%,.%'H, +*5#.Y&M%# 5*)*.)H# I&4#+,%,#'%, &4%)%.:T,+2 ".%50 ºC F ".%+:,+,F%% 1#,*1+%4*F % )%,.&,& 1*9&'(,& (8O9P< 7, a).
-* .#&1$%2 )# ".*,#1&'&, #+'%F .#&1$%*))*J +4#+% ".%+:,+,F*F&' ,*'(1* *5%) %I &1,%F%.:TM%3 &/#),*F – 1#,*1+%4 %'% +*'(1*9&'(,&(II). 8.#5"*'*Y%,#'()HJ 4#3&)%I4 .#&1$%% %I*9.&YU) )& 8O9P9 7. 8#.FH4 S&/*42F'2#,+2 1**.5%)&$%2 )%,.%'& 1 4#,&''*$#),.: (8O9P< 7, b), I&,#4 .#&1$%2 ".*,#1, "* 5F:4)&".&F'#)%24.!*5)*JFI&%4*5#J+,F:#,+,*.*)H,+)%,.%',1#,*1+%4*4+&1,%F%.*F&))HJ*9.&I*F&)%#41**.5%)&$%#J14-%4%)*&$%'1#,*1+%4)*/*1*9&'(,:(II),1*4"'#1+&1*9&'(,&(II) (8O9P< 7, c). ! 5.:/*J +,*.*)H, )%,.%' ".#,#."#F, /%5.*'%I 5* 1&.9*)*F*J1%+'*,H % &44%&1& (8O9P< 7, d).
D&,#4 ".*%+3*5%, .#&1$%2 ):1'#*K%'()*/* I&4#M#)%21#,*1+%4& )& &44%&1 + *9.&I*F&)%#4 &4%5%)*F*/* 1*4"'#1+& (8O9P< 7, e). D&1'T0%,#'()H4!11!!^,&"*4 2F'2#,+2 5#1**.5%)&$%2 &4%5%)*F*/* '%/&)5& I& +0U, #/* ".*,*)%.*F&)%2 +*9.&I*F&)%#4 &4%5%)%#F*J +*'%, FH"&5&TM#J F :+'*F%23 .#&1$%% F *+&5*1 (8O9P< 7, f) [31].7)&'*/%0)&2 .#&1$%2 F ".%+:,+,F%% )%1#'2(II) ".% 100 ºC, ".*,#1, 5&'(S# [33](8O9P< 8). ?9.&I:TM%#+2 &4%5%)H (8O9P< 8, a) .#&/%.:T, + 1**.5%)%.*F&))H4% 14#,&''*$#),.: )%,.%'&4% + *9.&I*F&)%#4 3#'&,)H3 1,3,5-,.%&I&"#),&5%#)*FH3 1*4"'#1+*F)%1#'2 (8O9P< 8, b).aRNi(NO3)2Me2C=NOHN–NH2 NO3RnPr,R = Me, Et,iPr nBu, CH Cl2NH2R3 en–[Ni(en)3](NO3)2HNHNcRRNH2 HNNHRHNNiNH2 H2O(NO3–)2Ni(NO3)2Me2C=NOH2 RCNbNHNHdRRRO2 HN–2 NH3OR!O9P< 8.
!%),#I 1,3,5-,.%&I&"#),&5%#)*FH3 1*4"'#1+*F )%1#'2(II) % &$%'&4%5*F.8*':0#))H# '%/&)5H 4*/:, 9H,( F 42/1%3 :+'*F%23 5#1**.5%)%.*F&)H % FH5#'#)H F0%+,*4 F%5# (8O9P< 8, c). 8.% 5#1**.5%)&$%% F ".%+:,+,F%% F*5H ,.%&I&"#),&5%#)H".#,#."#F&T, /%5.*'%I 5* &$%'&4%5*F (8O9P< 8, d). ; "*+'#5)## 5#+2,%'#,%# 3%4%2,.%&I&"#),&5%#)*F % %3 1*4"'#1+*F 2F'2#,+2 9:.)* .&IF%F&TM#J+2 *9'&+,(T )&:1% [39]F+'#5+,F%# F&Y)*+,% 5&))H3 +*#5%)#)%J 1&1 5'2 K&.4&1*'*/%% (*9'&5&T, +"#1,.*49%*'*/%0#+1*J &1,%F)*+,% [39]), ,&1 % 5'2 *./&)%0#+1*J 3%4%% (2F'2T,+2 ".#1:.+*.&4% 5'2+%),#I& /#,#.*$%1'*F [39] % 1&,&'%I&,*.&4% F .#&1$%23 1*)5#)+&$%% [59]).8*I5)## F 5&)):T .#&1$%T F ".%+:,+,F%% "&''&5%2(II) 9H'% F*F'#0#)H &.*4&,%0#+1%#)%,.%'H [35].
6H'% "*':0#)H 9%+-1,3,5-,.%&I&"#),&5%#)*FH# 1*4"'#1+# "&''&5%2(II), '%/&)5HF +F*9*5)*4 F%5# )# FH5#'#)H.;&Y)*J .#&1$%#J 2F'2#,+2 ".*4*,%.:#4HJ 1#,*1+%4&4% /%5.*'%I )%,.%'*F 5* &4%5*F.; ".%+:,+,F%% 1&,&'%,%0#+1%3 1*'%0#+,F 3'*.%5& $%)1&(II) % 1#,*1+%4& (0.65 % 2.75 4*'%!12!!+**,F#,+,F#))*) )%,.%'H F ".%+:,+F%% F*5H :+"#S)* % F 42/1%3 :+'*F%23 ".#F.&M&T,+2 F1&.9*1+&4%5H (8O9P< 9, a) [38].
8.% %+"*'(I*F&)%% ,*'(1* *5)*/* %I 1*4"*)#),*F1&,&'%,%0#+1*J +%+,#4H – 1#,*1+%4& %'% 3'*.%5& $%)1&(II) .#&1$%2 )# ".*,#1,. =#,&'()*4#3&)%I4 5&))*J .#&1$%% )# %I:0&'+2, *5)&1* &F,*.H ".#5"*'*Y%'%, 0,* )& "#.F*4 ^,&"#".*%+3*5%, +*0#,&)%# *1+%4& + )%,.%'*4 F):,.% 1**.5%)&$%*))*J +K#.H $%)1&(II) (8O9P< 9,b), I&,#4 "*':0%FS%J+2 4-%4%)*&$%'1#,*1+%4 ".#,#."#F, /%5.*'%I 5* &4%5& + .#/#)#.&$%#J*1+%4& (8O9P< 9, c).aZnCl2R'2C=NOHRNH2OR = Alk, ArR'2 = Me2, C4H8, C5H10R'2C=NOH[ZnII]ORHb[ZnII]cN–R'2C=NOH–[ZnII]H2OORNH2NCR'2!O9P< 9.
8.*4*,%.:#4HJ +%+,#4*J $%)1(II)-1#,*1+%4 /%5.*'%I )%,.%'*F.8*I5)## :5&'*+( :,*0)%,( ".#5"*'&/HJ 4#3&)%I4 .#&1$%% /%5.*'%I& F ".%+:,+,F%%)%1#'2(II) [22]. \,&'*5%)%,.%' ".#,#."#F, /%5.*'%I 5* +**,F#,+,F:TM#/* &4%5& F".%+:,+,F%% +*'#J )%1#'2(II) % ".*"&)-2-*)*1+%4&. ?9.&I:#,+2 1*4"'#1+ )%1#'2(II) + 5F:421**.5%)%.*F&))H4% &4%5&4% (!O9P< 10, a). >),#.4#5%&, 9H' %5#),%K%$%.*F&), *) 2F'2#,+2".*5:1,*4 +*0#,&)%2 4 ^1F *1+%4& + 2 ^1F )%,.%'&, 1*,*.HJ ,.%5#),&,)* 1**.5%)%.:#,+2 14#,&''*$#),.: (8O9P< 10, b) % 5&'## ".#,#."#F, /%5.*'%I + *9.&I*F&)%#4 &4%5& (8O9P< 10, !)[22].-&%9*'## ".%4#0&,#'()H4% ".*4*,%.:#4H4% *1+%4&4% ".#F.&M#)%24% )%,.%'*F2F'2T,+2 "*':0#)%# K,&'*$%&)%)*F % %3 1*4"'#1+*F.