Диссертация (1150306), страница 7
Текст из файла (страница 7)
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
26*9.&I:#, ".*5:1, 9%++*0#,&)%2 + 9#)I&4%5*1+%4*4 6 + )%I1%4% FH3*5&4%, & ".*5:1, +*0#,&)%2+ &$#,&4%5*1+%4*4 FH5#'%,( %I .#&1$%*))*J +4#+% F*F+# )# :5&'*+(.3.7 L<:<D;9:7R<=7> #-7P7AE<=7H<P7GED87PABO DEPQH9D8EF QH<;7AB(II);+# "*':0#))H# %4%)*1*4"'#1+H "'&,%)H(II) 9H'% *3&.&1,#.%I*F&)H + "*4*M(T1*4"'#1+& K%I%1*-3%4%0#+1%3 4#,*5*F &)&'%I&, 1*,*.HJ F1'T0&' F +#92 >C, AOG 1-, Z!>-!(N–()!(N=C)"#$%&+!(N=C)%&%'41!!!0O!-;G, Z7, B!R, G!7 (5'2 )#1*,*.H3 *9.&I$*F) % %I4#.#)%# ,#4"#.&,:.H .&I'*Y#)%2 F$&–13600,FU.5*J K&I#.600; >C +"#1,.&3 "*':0#))H3 +*#5%)#)%J 32–61 1**.5%)%.*F&))H# 1 "'&,%)#(II) %4%)H%4#T, "*'*+H *, +.#5)#J 5* +%'()*J %),#)+%F)*+,% F 5%&"&I*)# 0&+,*, 3496–3058 +4–1,3&.&1,#.)H# 5'2 F&'#),)H3 1*'#9&)%J N–H [87].
; +"#1,.&3 ,&1Y# +*5#.Y&,+2 *5)& %'% 5F#"*'*+H FH+*1*J %),#)+%F)*+,% F 5%&"&I*)# 1674–1588 +4–1, *,)*+2M%#+2 1 F&'#),)H41*'#9&)%24 C=N, 3&.&1,#.)H# 5'2 %4%)*&$%'%.*F&))H3 *1+%4*F (:78?AD7 10–12) [87].!"#100!(C–()) (%)!(N–()!(N=C)"#$%&+!(N=C)%&%'0$&–13600600(78?AED 10. >C +"#1,. 1*4"'#1+& 37.
8*'*+& b(C`N) )# ".*2F'2#,+2.8.*5:1,H4*)*+*0#,&)%2,"*':0#))H#":,U4".%+*#5%)#)%2&4%5*1+%4*F11**.5%)%.*F&))H4 1 "'&,%)#(II) ):;.,;3 )%,.%'&4 36–43 )# %4#T, F >C +"#1,.&3 "*'*+F&'#),)H3 1*'#9&)%J +F2I% C`N (:78?AD7 10 % 11). Z,* 2F'2#,+2 3&.&1,#.)*J 0#.,*J1*4"'#1+*F "'&,%)H(II), *,'%0&TM#J %3 *, +**,F#,+,F:TM%3 1*4"'#1+*F "'&,%)H(IV), F >C+"#1,.&3 1*,*.H3 .&++4&,.%F&2 "*'*+& ".*2F'2#,+2 [99]. ; *,'%0%# *, ".*%IF*5)H3):;.,;& )%,.%'*F, F >C +"#1,.&3 ".*5:1,*F 4*)*+*0#,&)%2, +*5#.Y&M%3 1**.5%)%.*F&))HJ5%4#,%'$%&)&4%5 (32 % 33), %4#T,+2 "*'*+H FH+*1*J %),#)+%F)*+,% + 0&+,*,*J 2312 %2295 +4–1, *,)*+2M%#+2 1 F&'#),)H4 1*'#9&)%24 C`N (:78?AED 12) [87].!!42!$%#100!(C–()) (%)!(N–()!(N=C)"#$%&+!(N=C)%&%'0$&–13600600(78?AED 11.
>C +"#1,. 1*4"'#1+& 42. 8*'*+& b(C`N) )# ".*2F'2#,+2.!"#100!(C–()!"#100) (%)!(C–()) (%)0!(N≡C)!(N–()!(N=C)"#$%&+!(N=C)%&%'!(N=C)$&–1 "#$%&600+!(N=C)(78?AED 12. >C +"#1,. 1*4"'#1+& [32](Cl).>4##,+2%&%'%),#)+%F)&2 "*'*+& b(C`N).3600!(N–()0; +"#1,.&3 AOG 1- ".*5:1,*F 9%++*0#,&)%2 [44](Cl)2–61, & ,&1Y# 1*4"'#1+*F 34 % 353600$&–16009H'* *9)&.:Y#)* "* *5)*4: )&9*.: +%/)&'*F, F ,* F.#42 1&1 F +"#1,.&3 ".*5:1,*F4*)*+*0#,&)%2 [32](Cl), [33](Cl), 36–43 ".%+:,+,F*F&'* "* 5F& )&9*.& +%/)&'*F F +**,)*S#)%%1:1 *, %4%)& % )%,.%'&.
R&.&1,#.)*J 0#.,*J )#3#'&,)H3 ".*5:1,*F 36–43 % 55–61 2F'2#,+2)&'%0%# F +'&9*4 "*'# 5F:3 :S%.#))H3 +%/)&'*F + %),#/.&'()H4 +**,)*S#)%#4 1:2,*,)*+2M%3+2 1 &,*4&4 F*5*.*5& %4%)*/.:""H NH % &4%5)*J /.:""H NH2 (:78?AED 13). ; ,*NHNH NH!43!!7.0 4.0Y#9.0F.#42 F +"#1,.&3 3#'&,)H3 ".*5:1,*FF +'&9*4 "*'# )&9'T5&T,+2 ,.% :S%.#))H3 +%/)&'&1.0 F!. ".+**,)*S#)%% 1:1:1 + .&I'%0)H4% 3%4%0#+1%4% +5F%/&4% &,*4*F F*5*.*5& &4%5)*J /.:""H$%#(:78?AED 14).ClClPtNm-CH + p-CHOHNHNOHNHNHHNNo-CHCH3HPhPhCH2NH29.04.06.0!. ".1.0(78?AED 13. !"#1,. AOG 1- F#M#+,F& 59.!"#ClHNClPtNNNH3CN(CH3)2NOHN(CH3)2NHCH3NHNH NH7.09.04.01.0!.
".(78?AED 14. !"#1,. AOG 1- F#M#+,F& 32.$%#Cl!%/)&'H &,*4*F F*5*.*5& &4%5)*J /.:""H FCl3#'&,)H31*4"'#1+&3 46–48 % 51–54, F $#'*4,PtNN &,*4*F F +**,F#,+,F:TM%3CH+4#M#)H *,)*+%,#'()* +%/)&'*F .&++4&,.%FH3)#3#'&,)H33OOH Hp-CH; +"#1,.&3".*5:1,&3 55–61 Fm-CH+'&9*#+ "*'#.1*4"'#1+*F% 35 +%/)&'H &,*4*F F*5*.*5&HHN [33](Cl)NNN +%'()*# "*'# ()&5%4#,%'&4%)*/.:""H+4#M#)H F 9*'##~0.3–0.4 4.5.) "* +.&F)#)%T +o-CHHNHNH2PhPhHCH2!!+%/)&'&4%44!+**,F#,+,F:TM%3&$#,&4%5*1+%4)H3".*%IF*5)H3[32](Cl)%34.=&))*#)&9'T5#)%# 4*Y#, 9H,( *9_2+)#)* ^1.&)%.:TM%4 ^KK#1,*4 K#)%'()*J /.:""H.
8*5*9)*#2F'#)%# ^1.&)%.*F&)%2 K#)%'()*J /.:""*J )&9'T5,+2 ,&1Y# % 5'2 1*4"'#1+*F 42 % 43, F+"#1,.&3 1*,*.H3 +%/)&'H )-!! % 3-!! +4#M#)H F 9*'## +%'()*# "*'# "* +.&F)#)%T ++**,F#,+,F:TM%4% +%/)&'&4% F 1$",+-%I*4#.&3 38 % 39 +**,F#,+,F#))* ()& ~0.4 4.5. 5'2 )$1)".*,*)*F % 0.2 4.5. 5'2 3-1"-".*,*)*F).;"*'*Y%,#'()*4.#Y%4#Z!>-O!-;G5'2%*))H3+*#5%)#)%J*1&I&'%+(3&.&1,#.%+,%0)H4% "%1% 1&,%*)*F [M – Cl]+ ([32]+ % [33]+), [M – 2Cl]2+ ([44]2+, [45]2+, [49]2+ %[50]2+), [M – 2NO3]2+ ([46]2+–[48]2+ % [51]2+–[54]2+) % K.&/4#),)H3 %*)*F [M – - – 2Cl]+ ([44]+,[45]+, [49]+ % [50]+), [M – - – 2NO3]+ ([46]+–[48]+ % [51]+–[54]+).
='2 )#%*))H3 1*4"'#1+*F 34–43% 55–61 3&.&1,#.%+,%0)H4% *1&I&'%+( "%1%, +**,F#,+,F:TM%# "+#F5*4*'#1:'2.)H4 %*)&4[M + NH4]+, [M + Na]+ % [M + K]+. 8*4%4* ^,*/*, F +"#1,.&3 ,&1Y# )&9'T5&'%+( K.&/4#),)H#%*)H [M – Cl]+, [M – 2Cl – H]+, "*5*9)H# K.&/4#),)H# %*)H 2F'2T,+2 ,%"%0)H4% 5'23'*.%5)H3 1*4"'#1+*F "'&,%)H(II). G#I:'(,&,H ^'#4#),)*/* &)&'%I& 5'2 F+#3 "*':0#))H31*4"'#1+*F +*/'&+:T,+2 + .&+0U,)H4% 5&))H4% 5'2 ".#5"*'&/H3 +,.:1,:..O*'#1:'2.)H# +,.:1,:.H 1*4"'#1+*F 34, 35, 37, 43, [45](Cl)2, [46](OTf)2, [50](Cl)2,[54](NO3)2, 55 % 59 9H'% :+,&)*F'#)H 4#,*5*4 G!7 (:78?AD7 15 % 16).
;+# 1**.5%)&$%*))H#"*'%^5.H "*1&IHF&T, ,%"%0):T "'*+1*-1F&5.&,):T /#*4#,.%T 1*4"'#1+*F. ;+# :/'H F*1.:/4#,&''*$#),.& "'&,%)H(II) 9'%I1% 1 90º (I& %+1'T0#)%#4 :/'*F N–Pt–N F 3#'&,)H3 1*4"'#1+&3).='%)H +F2I#J Pt–Cl, .&F)H# 2.2862(12)–2.3193(7) Å ,%"%0)H 5'2 +F2I#J PtII–Cl [89]. 7 5'%)H+F2I#J Pt–N%4%) % Pt–N*1+%4, .&F)H#, +**,F#,+,F#))*, 1.972(2)–2.033(3) Å % 1.9895(18)–2.020(7) Å,%4#T, I)&0#)%2, 3&.&1,#.)H# 5'2 +F2I#J PtII–N%4%) % PtII–N*1+%4 [19, 90]. ='%)H +F2I#J % :/'H F%4%)*&$%'%.*F&))H3 *1+%4&3 +*/'&+:T,+2 + .&)## "*':0#))H4% I)&0#)%24% 5'2 +3*Y%3%4%)*1*4"'#1+*F "'&,%)H(II) [14, 15, 19].; 3#'&,)H3 1*4"'#1+&3 34, 35, [45](Cl)2, [46](OTf)2, [50](Cl)2, [54](NO3)2 (:78?AED 15):/'H N–Pt–N )&3*52,+2 F 5%&"&I*)# 77.07(7)º–79.63(9)º.
; +*#5%)#)%23 [46](OTf)2, [54](NO3)2+F2I% C–N%4%) 2F'2T,+2 ,%"%0)H4% 5F*J)H4% +F2I24% +* I)&0#)%24% 5'%) 1.276(3)–1.2788(17) Å [16, 21, 49, 90]. ; ,* Y# F.#42, F 5%4#,%'$%&)&4%5)H3 ".*%IF*5)H3 34, 35,[45](Cl)2 % [50](Cl)2 5'%)H +F2I#J C–N%4%) %4#T, I)&0#)%2 1.298(3)–1.316(10) Å, & 5'%)H +F2I#JC–NMe2 – 1.314(11)–1.339(10) Å, 0,* +F%5#,#'(+,F:#, F "*'(I: ".*4#Y:,*0)*/* "*.251& %31.&,)*+,% F+'#5+,F%# +*".2Y#)%2 4#Y5: )%4%. >)*# +*".2Y#)%# 9H'* *9)&.:Y#)* 4#Y5:+F2I24% C–N*1+%4 % C–NH2 [1.3132(16)–1.330(3) Å % 1.314(3)–1.333(4) Å +**,F#,+,F#))*].
!F2I%!–? [1.3349(15)–1.363(10) Å] % ?–N [1.4446(14)–1.472(8) Å] 2F'2T,+2 ,%"%0)H4% *5%)&.)H4%+F2I24% [90].!!45!; +*#5%)#)%23 [45](Cl)2, [46](OTf)2, [50](Cl)2 *1+%4)HJ K.&/4#), ".% +F2I% C=N %4##,8-1*)K%/:.&$%T, & F 1*4"'#1+&3 34 % 35 – Z-1*)K%/:.&$%T. ; 3#'&,)*4 1*4"'#1+# [54](NO3)25F&%4%)*'%/&)5&%4#T,.&I'%0):T8/Z-1*)K%/:.&$%T.;8-%I*4#.&3%4##,+2F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( 4#Y5: *5)%4 %I &,*4*F F*5*.*5& /.:""H NH2 %*1+%4)H4 &,*4*4 1%+'*.*5& (N•••O 2.463–2.583 Å, :/*' N–H•••O 95.97–105.21º). ;+*#5%)#)%23 34 % 35, +*5#.Y&M%3 %4%)*'%/&)5H F Z-1*)K%/:.&$%%, F*5*.*5)&2 +F2I( %4##,+24#Y5: &,*4*4 F*5*.*5& /.:""H NH2 % &,*4*4 Cl (N•••Cl 3.099(4) % 3.092(3) Å, :/*' N–H•••Cl156.8º % 163.1º +**,F#,+,F#))*).
;):,.%4*'#1:'2.)H3 F*5*.*5)H3 +F2I#J F %4%)*'%/&)5#,%4#TM#4 Z-1*)K%/:.&$%T, F +,.:1,:.# [54](NO3)2 *9)&.:Y#)* )# 9H'*.3545 (Cl)2•H2O46 (OTf)234 • 1/4MeNO250 (Cl)2•31/2MeNO2 •1/2H2O54 (NO3)2 •MeNO2(78?AED 15. O*'#1:'2.)H# +,.:1,:.H 3#'&,)H3 1*4"'#1+*F.!!46!5*+-6%+3#'&,H [49]2+–[54]2+ %4#T, )#"'*+1*# +,.*#)%#. >+1&YU))&2 /#*4#,.%2*9:+'*F'%F, +:M#+,F*F&)%# 5&))H3 1*4"'#1+*F F F%5# *",%0#+1% &1,%F)H3 7- % 9-K*.4.?9# K*.4H +*#5%)#)%J [49]2+–[54]2+ 9H'% *9)&.:Y#)H + "*4*M(T G!7 .&$#4%0#+1%31.%+,&''*F [50](Cl)2 % [54](NO3)2. ; 1.%+,&''%0#+1%3 .#SU,1&3 9H'% *9)&.:Y#)H *9& %I*4#.&(:78?AED 16).HNHMe2N(Cl)2HPh PhHNO NPtNHN ONHNHHNMe2NO NMe2N(Cl)2HPh PhNHPtN ONHHNMe2P-isomerM-isomer(78?AED 16.