Диссертация (1150306), страница 5
Текст из файла (страница 5)
;+# +F2I% !(1)–N(1) 2F'2T,+2,%"%0)H4% 5F*J)H4% +F2I24%, %3 5'%)H )&3*52,+2 F 5%&"&I*)# 1.277(5)–1.310(4) Å [16, 21, 24,90]. !F2I% C–N F *1+%4)*J 0&+,% 4*'#1:'H %4#T, 5F*J)*J 3&.&1,#. [1.292(4)–1.305(2) Å] [16,21, 24, 90], F ,* F.#42 1&1 +F2I% !–? [1.331(8)–1.341(2) Å] % +F2I% ?–N [1.4658(18)–1.496(7) Å]2F'2T,+2 ,%"%0)H4% *5%)&.)H4% +F2I24% [90].
X.:""H NH2 % NMe2 (F 1*4"'#1+&3 15,16•aH2O, 17•2Me2CO % 17•2CHCl3) %4#T, &4%5)HJ 3&.&1,#., 0,* "*5,F#.Y5,+2 ".% &)&'%I#5'%) +**,F#,+,F:TM%3 +F2I#J !–N: 1.335(7)–1.361(8) Å 5'2 +F2I#J !–NH2 % 1.325(8)–1.336(6) Å5'2 +F2I#J !–NMe2 [90]. ; 8, 11, 13•2Me2CO % 14 %4%)*&$%'%.*F&))HJ *1+%4 )&3*5%,+2 F 81*)K%/:.&$%% (:78?AED 5), F 1*,*.*J )&9'T5,+2 F*5*.*5)&2 +F2I( 4#Y5: &,*4*4 F*5*.*5&%4%)*/.:""H % *1+%4)H4 &,*4*4 &I*,& (+**,F#,+,F:TM%# .&++,*2)%2 N•••N '#Y&, F 5%&"&I*)#2.542(3)–2.574(2) Å, & :/'H N–H•••N – 110.9–117.7º).
8*5*9)H# F*5*.*5)H# +F2I% .&)##)&9'T5&'%+( 5'2 4*)*5#),&,)* 1**.5%)%.*F&))H3 %4%)*&$%'%.*F&))H3 *1+%4*F [16, 21, 24,25, 49]. =.:/&2 F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( )&9'T5,+2 4#Y5: &,*4*4 F*5*.*5&&4%5)*J /.:""H % *1+%4)H4 &,*4*4 1%+'*.*5& [N•••O 2.510–2.553 Å, :/*' N–H•••O 94.92–107.31º]. -&".*,%F, F +,.:1,:.&3 15, 16•aH2O, 17•2Me2CO % 17•2CHCl3 '%/&)5H )&3*52,+2 F ZK*.4# (:78?AED 6), % 5'2 )%3 )&9'T5,+2 '%S( *5)& F):,.%4*'#1:'2.)&2 F*5*.*5)&2 +F2I( –4#Y5: &,*4*4 F*5*.*5& &4%5)*J /.:""H % &,*4*4 1%+'*.*5& *1+%4)*J /.:""H [N•••O 2.494–2.530 Å, :/*' N–H•••O 91.65–116.10º].!!27!813 • 2Me2CO1411(78?AED 5. O*'#1:'2.)H# +,.:1,:.H +*#5%)#)%J 8, 11, 13 % 14. >4%)*'%/&)5H %4#T, 81*)K%/:.&$%T.1517 • 2CHCl317 • 2Me2CO16 • 1/2H2O(78?AED 6.
O*'#1:'2.)H# +,.:1,:.H +*#5%)#)%J 15–17. >4%)*'%/&)5H %4#T, Z1*)K%/:.&$%T.!!28!2.4 /9DEE:G7A<=7> #-7P7AE<=7H<P7GED87PEF 7R Z78-#-7P7AE<=7H<P7GED87PABODEPQH9D8EF QH<;7AB(IV) 7 PEA7;E:7AS 7O G<HIA9CW7O Q:9F:<V9A7C8.*4*,%.:#4&2 "'&,%)*J(IV) .#&1$%2 +*0#,&)%2 )%,.%'*F + &4%5*1+%4&4% "*IF*'2#,"*':0%,( +,&9%'%I%.*F&))H# 4*)*5#),&,)* 1**.5%)%.*F&))H# %4%)H HN=C(R)ON=C(NH2)R'F 42/1%3 :+'*F%23.
='2 %I:0#)%2 %3 ".#F.&M#)%J F +F*9*5)*4 +*+,*2)%% )#*93*5%4* 9H'* %35#1**.5%)%.*F&,(. ='2 %3 FH+F*9*Y5#)%2 %I +*+,&F& 1*4"'#1+& )&4% 9H'% %+"*'(I*F&)H.&I)H# +"*+*9H, 1*,*.H# *"%+&)H )%Y#.-#+4*,.2 )& I)&0%,#'():T 1%)#,%0#+1:T %)#.,)*+,( 1*4"'#1+*F "'&,%)H(IV), %IF#+,)*)#+1*'(1* 4#,*5*F I&4#M#)%2 4*)*5#),&,)* 1**.5%)%.*F&))H3 %4%)*F [91-93] % /#,#.*$%1'*F+ K.&/4#),*4 !=N [94] ".% 5&))*4 4#,&''*$#),.#, *+)*F&))H3 )& .#&1$%% 1*4"'#1+*F +%I9H,1*4 "%.%5%)& [93, 94] % 5%K*+K%)*F [91, 92].
-&4% 9H'* *9)&.:Y#)*, 0,* F +*#5%)#)%237–17 .&)## )#%IF#+,)H# %4%)*'%/&)5H )&+,*'(1* ".*0)* :5#.Y%F&T,+2 4#,&''*$#),.*4, 0,*%3 5#1**.5%)&$%2 )# ".*%+3*5%, 5&Y# F .&+,F*.# "%.%5%)& ".% 85 ºC F ,#0#)%# +:,*1.-#+4*,.2 )& ^,*, .&)## +**9M&'*+(, 0,* 5'2 5#1**.5%)&$%% 3#'&,)H3 K*+K%)*F % /#,#.*$%1'*FF 1*4"'#1+&3 "'&,%)H(II) + :+"#3*4 9H'% ".%4#)#)H $%&)%5H M#'*0)H3 4#,&''*F [95-97]. ;5*"*')#)%# 1 ^,*4:, $%&)%5H )# %4#T, +%/)&'*F F +"#1,.&3 AOG 1-, 0,* 9'&/*".%2,+,F*F&'*9H 4*)%,*.%)/: ".#F.&M#)%J +F*9*5)H3 %4%)*F. ; +**,F#,+,F%% + ^,%4, )&4 :5&'*+(5#1**.5%)%.*F&,( %4%)H 19–25 %I 1*4"'#1+*F "'&,%)H(IV) 11–17 ":,U4 F*I5#J+,F%2 )&.&+,F*.H 1*4"'#1+*F F (!D3)2SO 6-1.&,)H4 %I9H,1*4 NaCN [95, 96].
=#1**.5%)&$%2 '%/&)5*F".*%+3*5%'& F ,#0#)%# )#+1*'(1%3 +#1:)5 ".% 1*4)&,)*J ,#4"#.&,:.# + *9.&I*F&)%#4+F*9*5)H3 4-%4%)*&$%'%.*F&))H3 &4%5*1+%4*F 19–25 (8O9P< 19, a).O*)%,*.%)/ ".#F.&M#)%J "*':0#))H3 %4%)*F *+:M#+,F'U) + "*4*M(T +"#1,.*+1*"%%AOG 1- %13!. 6H'* :+,&)*F'#)*, 0,* %4%)H 19–22 ".#,#."#F&T, ".#F.&M#)%2 "* 5F:4)&".&F'#)%24: $%1'%I&$%2 F +**,F#,+,F:TM%J 1,2,4-*1+&5%&I*' % .&+"&5 )& %+3*5)H# )%,.%' %&4%5*1+%4 (8O9P< 19, b % !).
?9.&I*F&)%# *1+&5%&I*'*F 9H'* "*5,F#.Y5#)* +.&F)#)%#4+"#1,.*F AOG 1- %13! .#&1$%*))H3 +4#+#J +* +"#1,.&4% /#,#.*$%1'*F, "*':0#))H3F+,.#0)H4 +%),#I*4 [98].-&4% ,&1Y# 9H'* *9)&.:Y#)*, 0,* 5*9&F'#)%# :1+:+)*J 1%+'*,H (2 4*'%) +.&I: "*+'#5#1**.5%)&$%% %4%)& )# F'%2#, )& 5&'()#JS%# ".#F.&M#)%2 %4%)*F. ; ,* Y# F.#425*9&F'#)%# +,#3%*4#,.%0#+1*/* 1*'%0#+,F& 9*'## +%'()*J "%1.%)*F*J 1%+'*,H +:M#+,F#))*:+1*.2#, .&I'*Y#)%# %4%)*F % 5#', %3 ".#F.&M#)%2 I)&0%,#'()* 4#)## +#'#1,%F)H4%.8*4%4* ^,*/*, 5*9&F'#)%# 1 4*'% ZnCl2 +"*+*9+,F:#, "*0,% 1*'%0#+,F#))*4: .&+"&5: %4%)*F)& %+3*5)H# )%,.%' % &4%5*1+%4.!!29!RH0.5 HNONR'ClCl HPt NNH Cl ClR'ONHHR11–17aN–Na2[Pt(CN)6]–NaClNaCNexcessR'Hc1 N–NH3RR'x1NObNONHH19–25R'NHON4–6x2NH2RRY 8E9G7A9A7>19202122232425REtEtEtPhNMe2NMe2NMe2R'MeCH2PhPhPhMeCH2PhPhNx10.120.230.320.19<0.03<0.03<0.03x20.880.770.680.81~0.04~0.04~0.04!O9P< 19.
=#1**.5%)&$%2 4-%4%)*&$%'&4%5*1+%4*F % %3 5&'()#JS%# ".#F.&M#)%2.-:4#.&$%2 +*#5%)#)%J % FH3*5H 1*)#0)H3 ".*5:1,*F ".%F#5#)H F ,&9'%$#.=&))H# AOG 1- "*1&IHF&T,, 0,* +*#5%)#)%2 23–25 "*+'# 5#1**.5%)&$%% + "#.%*5*4"*':.&+"&5& ~7 4%) ".#,#."#F&T, 1.&J)# )#+#'#1,%F)HJ .&+"&5. ; "*':0#))*J +4#+% F+'#5*FH3 1*'%0#+,F&3 9H'% 5#,#1,%.*F&)H %+3*5)H# &4%5*1+%4H % 5%4#,%'$%&)&4%5, & ,&1Y#+**,F#,+,F:TM%# 5-5%4#,%'&4%)*-1,2,4-*1+&5%&I*'H. ?+)*F)H4 1*4"*)#),*4 *9.&I:TM%3+2+4#+#J 2F'2'&+( 5%4#,%'4*0#F%)& (35, 32 % 30% *,)*+%,#'()* %+3*5)*/* 1*'%0#+,F& %4%)*F23–25 +**,F#,+,F#))*).
?+,&'()H# ".*5:1,H %5#),%K%$%.*F&)H )# 9H'%.8.% &)&'%I# "*':0#))H3 ^1+"#.%4#),&'()H3 5&))H3 "* .&+"&5: ".*"%*)%,.%'()H3".*%IF*5)H3 19–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–22 +%/)&' &,*4& F*5*.*5&%4%)*/.:""H )&3*5%,+2 F +'&9*4 "*'# (8.41–7.57 4.5.), F ,* F.#42 1&1 F +"#1,.&3 %4%)*F 23–25+%/)&' +**,F#,+,F:TM#/* &,*4& .&+"*'*Y#) F +.#5)#J *9'&+,% +"#1,.& (7.02–5.86 4.5.).!%/)&'H &,*4*F F*5*.*5& &4%5)*J /.:""H F I&F%+%4*+,% *, +,.:1,:.H %++'#5:#4*/* F#M#+,F&".#5+,&F'#)H F +"#1,.&3 '%9* *5)%4 :S%.#))H4 +%)/'#,*4 (19–22, 25), '%9* 5F:42*,5#'()H4% :S%.#))H4% +%)/'#,&4% (23 % 24).CH3HNH2H HHONHHHNHHHCH2Ho-CHm-CH + p-CHNH2NH9.00.06.0 3.0!.
".(78?AED 7. !"#1,. AOG 1- F#M#+,F& 21.>4%)H 23–25 9H'% *3&.&1,#.%I*F&)H ,*'(1* + "*4*M(T AOG 1- %I-I& 1*.*,1*/*F.#4#)%+:M#+,F*F&)%2,F,*F.#421&1+*#5%)#)%2*3&.&1,#.%I*F&)H + "*4*M(T AOG 13!{H} (:78?AED 8).19–229H'%5*"*')%,#'()*!!31!C6C7HC2C1HHHNH2H HC4OC3NNHHC5C6C6C7C7C8HHHC1C8C4C5C2[Pt(CN)6]2–C3!. ".2000(78?AED 8.
!"#1,. AOG 13C{H} F#M#+,F& 21.8.%9'%I%,#'()HJ "#.%*5 "*':.&+"&5& F#M#+,F 19–25 9H' :+,&)*F'#) )& *+)*F&)%% .25&+"#1,.*F AOG 1-, +)2,H3 5'2 1&Y5*/* F#M#+,F& 0#.#I .&F)H# ".*4#Y:,1% F.#4#)% (5'2 19–220#.#I 1&Y5H# 12 0; 5'2 23–25 + %),#.F&'*4 60 +).2.6 &:9GQEH<S<9PBC P9O<A7RP EZ:<REF<A7> 1,2,4-ED8<G7<REHEF?+)*FHF&2+( )& ^1+"#.%4#),&'()H3 % '%,#.&,:.)H3 5&))H3, 4H ".#5"*'&/, 0,*.#&1$%2 *9.&I*F&)%2 1,2,4-*1+&5%&I*'*F %I )%,.%'*F % &4%5*1+%4*F +*+,*%, %I 5F:3 ^,&"*F(8O9P< 20). 8#.FH4 ^,&"*4 2F'2#,+2 ):$"1*3)- ):1'#*K%'()*# ".%+*#5%)#)%# &4%5*1+%4& 1)%,.%':, F .#I:'(,&,# 1*,*.*/* F .&+,F*.# *9.&I:#,+2 .&F)*F#+)&2 1*)$#),.&$%2 O%4%)*&$%'&4%5*1%4& D (5'2 )#1&,&'%I%.:#4*J .#&1$%%) %'% ! (5'2 1&,&'%I%.:#4*J 4#,&''*4.#&1$%%).
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
6H'* *9)&.:Y#)*, 0,* F I&F%+%4*+,% *,".%.*5H )%,.%'& *9.&I:TM%#+2 %4%)*'%/&)5H +:M#+,F:T, F .&I'%0)H3 1*)K%/:.&$%23:".*%IF*5)H#&'1%'-%&.%'1&.9*)%,.%'*F–F8-1*)K%/:.&$%%,".*%IF*5)H#5%&'1%'$%&)&4%5*F – F Z-1*)K%/:.&$%%. Z,: .&I)%$: F 1*)K%/:.&$%23 4*Y)* *9_2+)%,(+,#.%0#+1%4%^KK#1,&4%I&4#+,%,#'#J,".#"2,+,F:TM%3)&3*Y5#)%T+,#.%0#+1%I&,.:5)U))*J /.:""H PtCl4 % 5%4#,%'&4%)*/.:""H F 5*+-"*'*Y#)%% 5.:/ 1 5.:/:.?9.&I:TM%#+2 %4%)H )&+,*'(1* ".*0)* +F2I&)H + 4#,&''*$#),.*4, 0,* %3 )# :5&U,+25#1**.5%)%.*F&,( 5&Y# F .&+,F*.# "%.%5%)& ".% 85 ºC F ,#0#)%# +:,*1.