pH-induced valence inversion in bio-inspired diiron complexes

Texte intégral

(1)pH-induced valence inversion in bio-inspired diiron complexes Ramachandran Balasubramanian. To cite this version: Ramachandran Balasubramanian. pH-induced valence inversion in bio-inspired diiron complexes. Inorganic chemistry. Université de Grenoble, 2013. English. �NNT : 2013GRENV080�. �tel-01555350�. HAL Id: tel-01555350 https://tel.archives-ouvertes.fr/tel-01555350 Submitted on 4 Jul 2017. HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés..

(2) THÈSE Pour obtenir le grade de. DOCTEUR DE L’UNIVERSITÉ DE GRENOBLE Spécialité : CHIMIE Arrêté ministériel : 7 août 2006. Présentée par. Ramachandran BALASUBRAMANIAN Thèse dirigée par Dr. Geneviève BLONDIN préparée au sein du Laboratoire de Chimie et Biologie des Métaux dans l'École Doctorale de Chimie et Sciences du Vivant. Inversion de valence induite par le pH dans des complexes à deux fer Thèse soutenue publiquement le 22 octobre 2013, devant le jury composé de :. Mr Bruno ANDRIOLETTI Professeur, Université Claude Bernard, Lyon, Rapporteur. Mr Yves LE MEST Directeur de Recherches CNRS, Université de Bretagne Occidentale, Brest, Rapporteur. Mme Carole DUBOC Directrice de Recherches CNRS, Université Joseph Fourier, Grenoble, Présidente. Mr Cyrille COSTENTIN Professeur, Université Paris Diderot – Paris 7, Paris, Examinateur. Mr Jean-Marc LATOUR Directeur de Recherches CEA, CEA, Grenoble, Examinateur. Mme Geneviève BLONDIN Directrice de Recherches CNRS, CEA, Grenoble, Directrice de thèse Université Joseph Fourier / Université Pierre Mendès France / Université Stendhal / Université de Savoie / Grenoble INP.

(3)

(4) . A cknowledgement Foremost, I would like to express my sincere gratitude to my advisor D r. Geneviève BLONDIN for the continuous support of my Ph.D study and research, for her patience, motivation, enthusiasm, and immense knowledge. Her guidance helped me in all the time of research and writing of this thesis. I could not have imagined having a better advisor and mentor for my Ph.D study. Besides my advisor, I would like to thank the rest of my thesis committee: Dr. Carole DUBOC, Dr. Lionel DUBOIS, and Dr. Jean-Marc LATOUR, for their encouragement and insightful comments over the project. My sincere thanks go to Prof. Cyrille COSTENTIN, Prof. Marc ROBERT and Prof. Jean-Michel SAVEANT of LEM group in Université Paris 7 for offering me an opportunity to perform electrochemical experiments in collaboration to the current project. I would like to thank my fellow lab mates in PMB group, CEA, Grenoble: Nathalie GON for teaching and helping me in chemical synthesis, Patrick DUBOURDEAUX for guiding me in chemical synthesis, NMR and UV-vis measurements, Eric GOURE for getting along with me and the project by sharing immense ideas and extensive support, Dr. Martin CLEMANCEY and Dr. Ricardo GARCIA-SERRES for Mössbauer, Colette LEBRUN for mass spectroscopy, Pierre-Alain BAYLE for NMR spectroscopy, In particular, I am grateful to Dr. Jean-Marc LATOUR for holding the team PMB together on all occasion and discussing science with each and everybody enthusiastically. I would also like to thank the other members in my lab that includes, Dr. Victor DUARTE and his cute family (Mme. Isabelle DUARTE, Quentin and Alisée), Dr. Olivier SENEQUE, Christelle CAUX-THANG, Vincent LEBRUN (PhD student), Aurélie JACQUES (PhD student), Manon ISAAC (PhD student), Alexandra SEVE (M2 student-UJF), Patricia SCHNEIDER (M2 student-UJF) for making each and every day lively and most I am going to miss will be the Group presentations, Friday breakfast, Christmas lunch, Birthdays parties, etc. My thanks also extend to all the staffs and members in CEA, Grenoble; CNRS-Délégation Alpes who made life simpler by providing resources and funds. A special thanks to head Mr. Stéphane MENAGE, LCBM, CEAGrenoble and other members for their active participation in the development of science. A special thanks to all the Indian colleagues in CEA, Grenoble: Dr. Ashok Kumar NANJUNDAN (Post-Doc) and his family, Dr. Senthilnathan DHURAIRAJAN (Post-Doc) and his family, Dr. Ramakrishnan SETHU (Post-Doc) and his family, Dr. Velavan KATHIRVELU (Post-Doc) and his family, Dr. Sabareesh VELU and his family, Dr. Govindh PRAJAPATHI (Post-Doc), Dr. Manikandan KARUPASAMY (Post-Doc) and his .

(5) . family, Dr. Saravanan RENGARJAN (Post-Doc) and his family, for sharing all the good will, trust, faith and made me to feel better at hard times.. Also my gratitude extends to fellow Indians inside and outside CEA (the list continues…), for your great support and participation in activities like weekend crickets, group lunch parties etc On the whole, my hearty wishes for each and every other mentioned above, to succeed in any future endeavors they come across and I pray god to shower you good health and wealth… Last but not the least; I would like to thank my family: my parents M r. Balasubramanian NAGARAJAN and M rs. Girija BALASUBRAMANIAN, for giving birth to me at the first place and supporting me throughout my life, my brother M r. Kalyanaraman BALASUBRAMANIAN for giving me immense support on everything and everyday.. Thank you Ramachandran BALASUBRAMANIAN. .

(6) . . .......................................................................................). .....................................................................................................2

(7)

(8)

(9)

(10)

(11) ! "

(12) # $%

(13) !

(14) %& ' # (

(15)

(16) !

(17) )

(18) *%+ ,

(19) %

(20)

(21) "

(22) , # -

(23) '

(24)

(25) . # "

(26) " . # *

(27) / 0 1'2

(28) '# 3 "

(29) ,. 2.%#'#"/#($ '%#"%"&%-&#)%,#'"#!".........32 ! 4

(30) 5%" 6

(31) / & 6

(32) 3 74%48

(33) & , . . *%9!"& :. !; & 6

(34) / *%' 2

(35) 4

(36) (

(37) 2

(38) , 5%"& : !; 6

(39) < 74%4 6

(40) #. #. . *%9!" 6

(41) #. / '

(42)

(43) 4

(44) (

(45) 2

(46) # .

(47) . / 74%48

(48) & # /. . *%9!"& ##. / !; & ## ( 6

(49) "

(50) #3 !

(51) 8

(52) =

(53) #3 '

(54) 3: # &

(55) %

(56)

(57)

(58) ,3 # - 1,, # & ) 2 :3 / "

(59) <.. 3.%#'#"/#($ '%#"%"&%- #*'&" (",'%#+ $#'"' "&'%"'#'$%'"%&.........................................................94 >2 2-</ '

(60) ?<, '

(61) ?. .....................................................................................................259 2. "&,"'&&................................................................................264 % %3% %% @A3/ % %3% %% @A3/ %@% A

(62) @#A33 # %@B%@% A%

(63) A%3% %% @/A33 / %@B%@% A%

(64) A%3% %% @3A3< 3 %@B%@% A%

(65) A%3% %% @,A3< , %@%

(66) A

(67) 6%9%@% A

(68) @:A,. : %@@% A%

(69) A%3%@%@%

(70) A

(71) 6%%@% A%

(72) %% @<A,.. . .

(73) . < %@@% A%

(74) A%3%@%@%

(75) A

(76) 6%%@% A%

(77) %% B *%

(78) 9*@.A, . @@% %

(79) 6 6 %%A A

(80) B*9@*6(!A@A, %@@@@% %

(81) 6 6 %%A A

(82) A A%3%@@@@ %% A A

(83) A A%#%

(84) B*%@6(!A@A@A, B3%@@@@% %

(85) 6 6 %%A A

(86) A A%#%

(87) B. *%. @6(!A#@A,# %@@@@% %

(88) 6 6 %%A A

(89) A A%#% %3%@@@%

(90)

(91) 6A@ A

(92) A A

(93) B*%@!6(A@A@9>A@#A,# # %@@@%

(94)

(95) 6A@

(96) %%% A

(97) A A%3%@@@@% %

(98) 6 6 % %A A

(99) A A%#%

(100) B*%@!6(A@A@9*A@/A,/ / %@%@% A%

(101) A%3%@@%

(102) 6 6 A%

(103) %% B *%@6(*A@A@,A,/. 3.#!$ +&,"'&&............................................................................277 C$(((@D% A$((@*9

(104) %AE@>#A,< CF%@6(*A@AG$(((@D% A$((E@>#A:. CF%@6(!A#G$(((@D% A$((E@>#A:. # CF%@6(!A@AG$(((@D% A$((E@>#A: / CF%@6(!A@A@

(105) 9*G$(((@D% A$((E@>#A:.

(106)

(107) .......................................................................................285

(108)

(109) ......................................................................................286 . .

(110)

(111) . &'#%)'#"& 8>. 8 . 8 . 8 )

(112) ). . 8 . 8. @% A

(113) . '.

(114) '

(115)

(116) ). *. '

(117) . >.

(118)

(119) . *9. 8

(120) . . )

(121) . .

(122)

(123) %

(124)

(125) . BB B. ' B&

(126) ) B B! 2

(127) *%9!" . '!$. ' . .

(128) %

(129)

(130) . +. +

(131) . +2. +2

(132) . .

(133) 9 !)

(134) "

(135)

(136) . *%9!". (4 . (

(137) 4

(138) )

(139) . H(. H

(140) ( . . )

(141) . !0 ! ! -) @)I A. 2. . !

(142) . !!>. !

(143) !

(144) >)

(145) . . %

(146)

(147)

(148) . 9&>#. & . 9*#. & . 9*>. &

(149) . 9 .

(150) . 9*. 9 * )

(151) .

(152)

(153) . $3. * . .

(154) %

(155)

(156) . .

(157) %

(158)

(159) . 8. 8 . >.

(160) . "9". " 9 " . .

(161) . . 2

(162)

(163) . &>.

(164) . &>'. & > ' . &. &

(165) . .

(166) ) . *$.

(167) . 8. % %

(168) . 74. 7 %4 . - . 0 . . 2 .

(169) . . .

(170) . . . . . . .

(171) . . .

(172) . . 8 #K+* +L) ,+ .L ,# ,,0&+L&,+ % *&1L07 &1 L%L )&$+ L7. *7 #4,0 ,+ . ,6&L&,+1LL ,#* L),4 0+,L% 0D%K1?G .L,0)&$+11K%1+J1L&)&8 ),5 ,6&L&,+1LL 1M5% 0 1%&$%,6&L&,+1LL 10 #4,0 7?G,+,0)&$+11K%1#)K,0& ,0 +&,+&,67$ +,+,01D *.)&&L&+L%&1,+ .L&1L% & L%L% *&)*,&#&L&,+,#L% )&$+ *7 %+$ &L1 )&$L&+$ .0,. 0L& 1M + L% 0 7 *,&#7 L% 0 KL&,+ .,L +L&) ,# L% * L) L, 5%&%&L&1,,0&+L D0,L,+L&,+,0 .0,L,+L&,+,#L% )&$+L1&L + 0,00 *,L #0,* L% * L)H)&$+ ,+ &1 1&*.) M 0 4 01&) * L%, ,# *,&#&L&,+M + + &+#)K + 0*L&))7L% 0 ,6.,L +L&),#* L),K+L,L% )&$+15 ))1&+#)K +&+$L% 1.&+1LL D . % %+$ ,# * L) 0 ,6 1LL &1 +L0) L, &+,0$+& % *&1L07 &+$ &+4,)4 &+ 5& . 0+$ ,#,*&+1,#% *&1L071L0L&+$#0,*L)71&1L,,00,1&,++#0,**L 0&)1L,&,),$7D ,#,0L% 1 ,#K+ 01L+&+$L% ## L1,+L% 0 ,6.,L +L&)1M# 5)&L 0LK0 &))K1L0L&,+1,+ &## 0 +L * L)),.0,L &+1 0 .0 1 +L 0& #)7 &+ L% #,)),5&+$ 1K &4&1&,+1 4&8D L% ) L0,+ L0+1# 0 &+ )K ,.. 0 .0,L &+1M . + +7 &+ F+ 1K. 0,6& &1*KL1 1M + .0,L,+G ,K.) ) L0,+L0+1# 01D . D. $,*'&*&+*;!0%($',!$-'((**',"&+. . *.,0L+L.0, 11 1&+&,),$70 0 ,60 L&,+1D+ +/K,L #,0 6*.) 0 1.&0L&,+. + .%,L,17+L% 1&1D , %& 4 M L% 1 0 ,6 0 L&,+1 0 /K&0 L% 1 LK. ,# + ) L0,+ L0+1.,0L%&++1. &#&.0,L &+10 4,L L,L%&1L1(D85 ))G(+,5+ 6*.) ,#L%&1)11 ,#.0,L &+1L%L007,KL ) L0,+L0+1.,0L&1L% )K ,.. 0.0,L &+1JNKD% NGL7. ,+L&+1 1&+$) ,.. 0&,+D% 70 +* K.0 ,6&+17+),$75&L%# 00 ,6&+1L%L0 &0,+.0,L &+1 )1, 11K*&+$ ) L0,+ L0+1# 01D 6*.) 1 ,# K.0 ,6&+1 0 8K0&+1 + 1L ))7+&+1D % L&4 1&L ,#L% 8K0&+#0,*

(173) &11%,5+&+&$K0 NDND. J.

(174) . . . . . . K H&1L+ &+ K H&1L+ &+. KH &1OP. QDNO. QDRS. KH &1NNT. QDNU. QDRO. KH71NNQ. QDQT. QDQP. KH. JDNT. JDNQ. JDNR. QDSU. LNQN. KH )7OU . . . " -*D7D7,".+",',! 2-*"&=*/&*'%G>7

(175) ,$;$" &"+,&+* JQK ,!'+%+-*,( NL7L 7. . % ,.. 0&,+&1&+L0&$,+)&.70*&) +4&0,+* +LD +L% /KL,0&).)+ ML% * L)&1. ,,0&+L 7L5,%&1L&&+ 1M+* )7 &1OP+ &1NNTM+,+ 71L &+ M71NNQD% L5,6&) .,1&L&,+1 0 ,K.& 7 *,0 0 *,L L,*1M L% 1K)#K0 L,* ,# L% * L%&,+&+ NQN + L% (,+ 0,+7) ,67$ + L,* ,# $)7&+ 0 1&K J )7OUKD %&1 1L0,+$ ,,0&+L&,+ 7 L%0 )&$+1 &+ L% /KL,0&) .)+ + L% .0 1 + ,# ,+ 5 ( 0 6&) ,,0&+L&,+ 0 ,**,+ # LK0 1,#K.0 ,6&+1JJKD % L&4 1&L 1%K##) 1 L5 +K +K ,6&L&,+1LL 1D% 1L0KLK0 .&L ,4 . . &1 + &L% 0 ,.L&*&8 #,0 L% ,6&&8 1LL +,0 #,0 L% 0 K ,+ D + &L&,+M %70,$ + ,+ + L5,0(*( 1L% 1L0KLK0 /K&L 0&$&M5&L%,+)71*))%+$ 1K.,+0 ,6&+L 0,+4 01&,+J1 &$K0 NDN #,0 L% KG)&$+ &1L+ 1 &+ 8K0&+KD %&1 *( 1 L% L&4 1&L 5 )) .L #,0 ) L0,+L0+1# 0D . E. *','& ""$",1&

(176) ,$'0',&,"$ ($'. . % % !. K. 06& &1*KL1 1 J1K L)78 L% &1.0,.,0L&,+L&,+ ,# L% 1K. 0,6& 0&). +&,+QIH&+L,&,67$ ++%70,$ +. 0,6& D+ ,KL,#L% L%0 #*&)& 1,#1&1 G,0 +G . + +LD% 1 .0,L &+11%0 1L0KLK0)+*&+,G&1 /K + %,*,),$7D%&) 1,* * * 01 ,# L%&1 #*&)7 0 ,+)7 L&4 5&L% J 1K ,0 + J+1KM ,L% 01 &1.)7 1&$+&#&+LL&4&L75&L%,L%* L)1J*&)&1L& F+1KD% 1 &## 0 + 1%4 ++& )7. O.

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

(178) &>="&*# *1> 7. . K0&+$ L)71&1M L% * L) &,+ 7) 1 L5 + L% V + V ,6&L&,+ 1LL 1D ,0 . .0 &1 )7M &L &1 .0,.,1 L%L L% L&4 1&L $, 1 ( + #,0L% L5 + H Q + H ,0&+$L,L% #,)),5&+$0 L&,+1C H QVQIHV V→ H V QQ H VQIHV V→ H QVQ. N. % * L)&+.0 +L% 1&1&1L% .%71&,),$&),+ D% * L)&+&L #&01L&1L% ,+ L%L%1. +&+,0.,0L &+. L% .0,L &+D,NJQK1L+1#,0L% 1. &#&Q#&)) 5&L%ND. U.

(179) . . % 0 ,6.,L +L&)1L. WT#,0L% ,6&L&,++L% 0 KL&,+,#L% 1K. 0,6& &,+0 /K)L,RDXS+HRDNP M0 1. L&4 )7JUKD% 1 4)K 10 &+&L ,+&$K0 QDQ1)K . )&+ 1D, ##&& +LML% L&4 1&L ,#1*K1L.0 1 +L0 ,6.,L +L&))7&+$ L5 +L% 1 4)K 1D + ML% 4)K 1#,0+J+K+ J K5 0 L 0*&+ ),1 L,RDJ+RDN M0 1. L&4 )7D. . " -*E7E7

(180) ,$"'&*-,"'&%"('"&,(',&,"$+'*+=$* *&+)-*>&

(181) &+=$* ("&#"+#> /!&"$$/",!=*+%$$+)-*>'*

(182) &=."'$,+%$$"+#>7!*'0(',&,"$+'*,!'0","'&&,! *-,"'&',!+-(*'0""'&*$+'"&",=(,*'%*=G>>7. . % % 6G/K ,*.) 6 1M +* )7 L+J QKPYJVFQV + L J QKPYJVFQVM .0 1 +L 0 KL&,+. *&.,&+L.,L +L&)1JK,#NDU+RDTT M0 1. L&4 )7J1 &$K0 QDQKD&*&)0&## 0 + 1 L5 + + F + . F . 5 0 ,1 04 &+ ,L% 0 ,*.) 6 1D 8 1&*&)0 &## 0 + &1 L%K1. +L&&.L #,0 L% 1* .0,L &+ 1K1L&LKL 7 &L% 0 + ,0 D 8,0&+$ L, L% * 1K0 *&.,&+L.,L +L&)1M,+ + K L%LL% +G1. &#&.0,L &+1 0 1 7%K+0 1 ,#*&))&4,)L1M*K%*,0 L%+L% G1. &#&.0,L &+1J,*.0 &+&$K0 QDQL% L%&(0,5+ +L%&+$0 +00,51#,0++ M0 1. L&4 )7KD8++ G0+ 1&)) 0#K0L% 0%7.,L% 1&8 L%L L% 1 .0 11&,+15&))) L,L,,),54)K #,0 J+K+L,,%&$%,+ #,0+J K J1 &$K0 QDQKD% $0,K.,#8DGD&)) 0+& )7 *,+1L0L 1L%0,K$%,*&+L&,+,#*KLL&,+1 7+1LK& 1ML%LL% *,K)L&,+,#L% 0 ,6.,L +L&)&1K L,L% %70,$ +,+ &+L 0L&,+ L5 + L% ,,0&+L 1,)4 +L *,) K) + L% $)KL*&+ 0 1&K L%L &+ P.

(183) . ,+L0,)1L% &)&L7L,.0,L,+L L% ,,0&+L %70,6& &,+&11K #0,*L% ,,0&+L 5L 0 *,) K) D ($( . !%!. 8,0&+$ L, L% 4)K 1 0 .,0L &+ &$K0 QDQM L J QKPYQV &1 1& 0 L, ,6&&8 L%+ L% . +),$,K1L+J QKPYQV,*.) 6D . &## 0 + 1&+L% 4)K 10 )1,,1 04 L5 +L% 1 #,K0,*.) 6 1D% 4)K 1. 11,&L L,L% 0 L&,+$&4 +&+/DNDN0 )&1L &+) QDNJPKD . . LJ QKPY+V→LJ QKUJ KYJ+GNKVV V. /DNDN. $E7D7 .$-+++'",,',!?

(184) = E>I@&M9?

(185) = E>H= >@=&;D>M'-($+=

(186) N

(187) &45&NE4F>7. +↓ →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

(189) * 1D7 0%1&+4 1L&$L L% ,6&L&,+,#&%70,+L%0 + J 8KL,. +L%0 + 7 L% *,+,+K) 0 &*&8,)&+. JXK. . ,*.) 6 L J Q&*KQJ &*KYQV 5% 0 Q&* W QMQEG&G. D %+&1L&1LK& 11K$$ 1LL% #,0*L&,+,#L% *,+,+L%0 +7)0&) 8I,+. L% #&01L1L .J1 &$K0 JDNKD . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(190) . . " -*F7D7"*+,+,(',!'0","'&'"!1*'&,!*&= >1,!%'&'&-$* '%($0. EM. ? = E"%>E= "%>@ =&', "%>7. . X. % #,)),5&+$$0.%11K**0&8 L% L% 0*,7+*&LD. .

(191) . . . .

(192) . 8 .

(193) . . 8 .

(194) . . .

(195) . . 8

(196) . . 8. . ;D. " -*F7E7 4*'0(',&,"$="& **'&"-%9**'&>&'&"++'","'&&* "+="&#$7%'$ >'* ,!"*'&'%($0+&"!1*'&,!*&7. . % 4)K 1 #,0 Z% + )K)L #,0 L% L%0 * %+&1*1 ,0&+$ L, L% ,4 . L% 0*,7+*& L J1 &$K0 JDJKD % 7 %4 L, ,*.0 5&L% L% L&4L&,+ + 0$7 ZWQQ()D*,)HN JXKD &+ L% 4)K 1 #,0 Z% L 0*&+ #,0 L% + * %+&1*1 0 )0$ 0L%+L% L&4L&,+00& 0ML% 1 .0, 11 1+ &10 D,L%&1,K015&L%&+ ,+ 0L .0, 11D.

(197) 8. .

(198) 8 . . .

(199) 8 . . .

(200) 8 . . &. ;D. " -*F7F7* .$-+="&#$7%'$ >'*,!,!*%!&"+%+7. . % 1 ,+1& 0L&,+1 +EL )571 + ,+ + L% &+L0&+1& .0, 11 &1 ,#L + &##&K)L L,. L 0*&+ D 5, 1 /K +L&) * %+&1*1 %4 + *,+1L0L #,0 L% 0 ) 1 ,# L% %70,/K&+,+ Q &+ L% .%,L,17+L% L& 0 L&,+ +L 0 ,# J1 &$K0 JDOKJSMNRKD

(201) 8 . .

(202) 8 .

(203) 8

(204) 8 . . ν.

(205) 8 .

(206) 8 .

(207) 8 .

(208) 8 .

(209) 8 .

(210) 8 . . " -*F7G7-%%*1',!*,"'&+)-&"&,!(!','+1&,!,"*,"'&&,*'

(211) +, * ."&"& ,/'+)-&,"$(*'+++=D &F $"&+>7!!1*')-"&'& E"+*$+,*(*','&,"'&1 ,!&*1*'01$""$-EDE7*','&+'*" "&,*'%,!1,'($+%&*&,+,-"+."&#1*'$'* ,!&*1 "+DEI& "+DEK7. . S.

(212) . 8+ * %+&1* %1 + & +L&#& #,0 L% 0 L&,+ L5 + K + 1 . . ,*.) 6 1JTKD %&1 &1 K L, L% %&$% &&L7 ,# GLK J.7KQJ.7KJ KYJV L%L .0 4 +L1 * %+&1*JNNKD #

(213) . $% "

(214) $$ $$$ " . $$$ "

(215) $$$ . $$$ . . " -*F7H7)-&,"$%!&"+%"&,"""&""%"-%=( OI7E>7. . % L5, 6*.) 1$&4 +,4 &+ 0 #) LL% L5,*',0L7. 1,#171L *1L%L%4 +. &+4 1L&$L C J&K ,0$+& 171L *1 1K% 1 /K&+,+ 1 KL )1, .% +,)1 + J&&K * L) ,*.) 6 1 *&+)7 1 ,+ 1 ,+ J1K% 1 0KL% +&K*K ,0 L%&0 J1K% 1 ,1*&K*K 0,5 L0+1&L&,+ * L)1D ,0 0 +L)7ML% 0,) ,#%70,$ +,+&+L% ,6&L&,+,#.% +,)1%1)1, +&+4 1L&$L M &+0 )L&,+5&L%L% ,6&L&,+,#L% 70,1&+ 0 1&K &+L% .%,L,171L * JNQKD . G. /'0%($+'"&""*'&*',"&+ )$'. .

(216)

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α+βM+ ,+L&+&+K) 0* L))K1L 0#,0L)71&1D)11 10 /K&0 8,G,)*&+ 5%&) )11 NR. .

(218) . 1,+L&+ OO)K1L 0D)11 &1#K0L% 0&4& &+L%0 1K)11 1D1,#)11 ,+L&+ &&0,+ )K1L 0M )11 &*+$+ 1 ,+ M + )11 % L 0, &0,+G*+$+ 1 171L *D + )11 1 + ML70,1&+ &111,&L L,L% &* L))&)K1L 0D. . . . " -*G7E7'(6:*1+,*-,-*',!*-=$,>&'0""2=*" !,>""*'&+",'$++ +7',,'%6 *'('+%!&"+%'*,! &*,"'&',!,1*'+1$*"$"&$++ +7*'('+%"&,&&',! ','*+"+/*",,&"&*/!"$,!0,**-"& &,+*"&","&$-7 *&+" &,,!β β =DG> +--&",&,!++%$1','*4*+(,".$1 7. . % &&0,+)K1L 0&+)11 &1),L &+L% β1KK+&L+&L1*&+0,) &1L,$ + 0L . K.,+,67$ +L&4L&,++1L&)&8 L70,1&+ 0&)JNQQIKD% 0&)&+&L&))7),L ,+L% L70,1&+ NQQ &+ L% β 1KK+&L &1 L% + L0+1),L L, L% 71L &+ OJS ,# L% α 1KK+&L 7 *K)L&1L . ,# %,) F ) L0,+ %,..&+$ * %+&1* ,4 0 [JU &1L+ D 0,L,+ L0+1# 0 0 L&,+1 0 ,K.) L,L%&10&)*&$0L&,+J1 &$K0 ODJKD. NN.

(219) . . .

(220) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . α. β. .

(221)

(222) . . . . . <. . " -*G7F7'(6*'('+*"$,*&+$',"'&(,!/1*'%,!DEE "&,!β β +--&",,'GFL"&,!α+--&",7 "&,!*"+&'"*,."&'*,!"&.'$.%&,'GK&EFJ"&,!"+(,!/14,!1*+!'/&"& *17 =DH> ',,'%6"$,*&+$',"'&7!*+,"& +,,',!','*"&,!β+--&","++!'/&'&,!$, 7. .

(223) ,8++ LK M

(224) D0L&+,))&+$ 0M01L + 0 1+,5,0( 01%4 +& )7 *,+1L0L . &+4 070 +L.. 0JNUKL%LM&+L% ( 7#&01L1L .,#L% 0 KL&,+,#NQQIML% 5L 0*,) K) ,,0&+L L,L% N1&L L%L&1L% ),1 1L&0,+1&L L,L% L70,1&+ 0 1&K M&+ L0+1# 01,+ .0,L,+L,7& )L% + KL0)L70,1&+ 0 1&K D% 1 /K + ,0 0&11L&))K+(+,5+D )$( . ". * 07L%0&+&1+,67$ +00& 0#,K+&+1 4 0)&+4 0L 0L 1D L1L&4 1&L ,+L&+1L5,. &0,+ +L 010&$ 7,+ 1.0LL +,+ $)KL*L D +L% ,67#,0*ML% L5,&0,+&,+10 &+ L% V 0 ,6 1LL + 0&$ 7 + 6L0 %70,6& D + ,# L% &0,+ +L 01 &1 . +L,,0&+L 5&L%L5,,,0&+L %&1L&&+ 15%&) L% ,L% 0&0,+ +L 0&1% 6,,0&+L 5&L%L%0 %&1L&&+ 1J1 ) #L.0L,#&$K0 ODOKD% #&6L&,+,#&,67$ +) 1L,L% #,0*L&,+,# L% ,67 #,0* 5% 0 L% L5, &0,+ L,*1 %4 + ,6&&8 L, L% V ,6&L&,+ 1LL + 0 0&$ 7+,6,$0,K.J1 0&$%L.0L,#&$K0 ODOKD8%70,. 0,6,+&,+&1 +G,+,,0&+L L, L% &0,+ 1&L 0&+$ L5, %&1L&&+ 1D % %70,. 0,6, )&$+ &1 %70,$ + ,+ L, L% ,6, 0&$ NQ. JNPK. D.

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

(226) . . . .

(227) . .

(228)

(229)

(230) .

(231) . 8 .

(232) . 8 .

(233) .

(234) . .

(235) . .

(236) .

(237) . .

(238) . 8 . . .

(239) . .

(240) . 8 .

(241) . .

(242)

(243) . . . " -*G7H7!"*&,'*%+'!%*1,!*"&&,!"&,*'&.*+"'&,/&,!+%"%,'*%+-('&( .*","'&+7. NJ.

(244) . H. '*#.$'("&,!!. . % $0,K. ,#

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eIII OO. NN. O. NN. – H+. FeII OO. +. + H+ N H2. N. FeII OO. NN. O. FeIII OO. N H. . " -*H7D7.*+"$"&,*.$&!* ,*&+*,*" *1=>(*','&,"'&',!,*%"&$&"$"&=&"$"> $" &7. . %&1 0 L&,+ &1 1&*&)0 L, L%L ,1 04 L5 + L% L5, 1 *&* L #,0*1 ,# % * 07L%0&+. J1 1 L&,+ODQKD%&1&1L,*7(+,5) $ L% 1&+$) 6*.) ,#4) + &+4 01&,+L0&$$ 0 7 . 40&L&,+1&+&,),$&)171L *1D8117+L% L&,*.) 6 10 ,+ 0+ M1&*&)00 L&,+%1 +,1 04 #,01&+$) % L 0,&+K) 00KL% +&K*G,1*&K*,*.) 6JQPKD. NO.

(246) . . . . . . . . . . . . . . . . . . . . . . . . . .

(247)

(248). . . . . . . . . . . " -*H7E7$&"&.*+"'&"&-1( "&*+/!&+,*,"& *'%. HM +, ?=,(1>=(1>+ =P:G4G8:(1>- =(1>E= E>@ =D $"&>'**'%,!'&:$,*'&'0""2+("+. HM & ?=,(1>=(1>+ =P:G4G8:(1>- =(1>E= >@ =E $"&>7,(1NE4E86I4E88:,*(1*""&4(1NE4E8:"(1*""&4 G4G8:(1NG4G8:"(1*""&7. . . L 1%,K) +,L& L%L .0,L,+G,K.) ) L0,+ L0+1# 0 &+4,)4&+$ + +&)&+ F+&)& . ,*.) 6%1 +&+4 1L&$L &+$0 L L&)17

(249) * 1D7 0+,5,0( 01JQTKD% 0 L&,+ &1 %70,$ + L,* L0+1# 0 L5 + L% ,*.) 6 1 LJ.KJ)KQ1 J Q%KY + LJ.KJ)KQ1 J %KY J.H W %70,L0&1JNG.708,)7)K,0L KD %&1 1LK7 &1 0 *0() &+ L%L )) L% #&4 0 )L 1 )#G 6%+$ 0L ,+1L+L1%4 + L 0*&+ 1L% L% 0*,% *&)LD. . . . " -*H7F7,'&+,&,+&,!*%'1&%",'*,! *,"'&,/&?=(>=$>E+ = !>@&. ?=(>=$>E+ = E !>@7#&*'%*=EJ>7. NU.

(250) . . L51,+)K L%LL% 0 L&,+.0, 14&,+ 0L .0, 11 6 .L&#L0 1,#&. ,01 0 .0 1 +L5 0 L% 1 /K +L&).L%57,0.0 4&)1D . +QRNNML% 8$ + L&,+) ) % 0% #K+

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

(253) D & &)&,M

(254) D D &+() 0M D D 07C ) L0,+ LK++ )&+$ &+ 1&+$) 071L)1 ,#. LQY LJY LOY.

(255) 8K0&+1D$$$$ECCDM&'(MNNPQJGNNPJND D ++&1,+C +4 1L&$L&+$ L% 1L0KLK0 + #K+L&,+ ,# K.0 ,6&+1D $ $ $ ECCHM')-MJRQUGJRUOD 8DGD &)) 0C ,6 LK+&+$ ,4 0 )*,1L N &+ 1L0KLK0))7 ,+1 04 L&4 1&L C 11,+1 #0,* G,+L&+&+$1K. 0,6& &1*KL1 D$$ $ECCKM)&MURNGUNRD NT.

(256) . LUY LPY. LTY LXY LSY. DD57 0M

(257) DD) +L&+ C ,51K. 0&11K. 0,6& ]$$ $DLKDM&)MJSJGORRD

(258) D&MDD&1% 0M

(259) DD% +MD1%#,0MD,,) *+C)K)L&,+,#0 ,6.,L +L&)1+ . 4)K 1 ,# %70L L0+1&L&,+ * L) L&,+1 7 ,*&+ +1&L7 #K+L&,+) + ,+L&+KK*& ) L0&L% ,07D$$DLLIM(*MOPSOGOTRQD D DD K7+%MD

(260) D 7 0C0,L,+G,K.) ) L0,+L0+1# 0D$ $ECCJM&%+MURROG URPOD

(261) DD7 0C0,L,+G,K.) ) L0,+L0+1# 0C80 L&,+% *&1L^14& 5D$ $

(262) "$ $ECCGM**MJPJGJSRD D D (*K0M D D ,(M D D 0&$ M D % 0C 0,L,+ + ) L0,+ L0+1# 0 &+. L 0&)0 L&,+ +L 01D$"$ECCCM&)*,MNOXGNPJD LNRY D D ,(M D $) M 8D %0+&M

(263) D D LL7M D % 0M D D (*K0C %+&1* ,# .0,L,+L0+1# 0&+%&&L&,+7QV&+&+$L,L 0&)0 L&,+ +L 01C L 0*&+L&,+,#L% . ,##K+L&,+))7&*.,0L+L%&1L&&+ 0 1&K 1D"ECCFM)'MSPQPGSPJQD LNNY DD KMD8D&+1L MD

(264) D 7 0C %+&1L&&*.)&L&,+1,#.0,L,+L0+1# 0,K.) L, ) L0,+L0+1# 0D$$$$ECCDM&'(MNRUJUGNRUOOD LNQY

(265) D,+&+MD,1L +L&+MD, 0LM

(266) DGD4"+LMD0C 70,$ +G,+0 )71&+,+ 0L .0,L,+G ) L0,+L0+1# 01D$$ $ECDEM)*MJTQGJXND LNJY DD,$+C),1&+$L% &0) ,+0&,+K) ,L& 0 KL1 1D $$ $$ECDDM&,M QUNGQUJD LNOY

(267) D8D,L0K4,

(268) 0DM

(269) DLK C)11 0&,+K) ,L& 0 KL1 1C L)),,#L,011 *)7+ 0 .&0&+4&L0,+&+4&4,D$ $$ECDDM,%MTJJGTPTD LNUY D -01-0# 0M D 8D ,++ 0M D ,(,7*M

(270) D &4M D 7 17*,1LM D

(271) &+$M 8D &)(,4M

(272) D LK M

(273) D D ,))&+$ 0

(274) 0DM D 0 1C K+L&,+ ,# L% &&0,+ )K1L 0 ,# )11 0&,+K) ,L& 0 KL1 &+.0,L,+G,K.) ) L0,+L0+1# 0D$$$$ ECDFM&(*MXUXUGXUSJD LNPY DDL +(*.C&,67$ ++% * 07L%0&+D$ $DLLGM-)MTNUGTQPD LNTY D D ,(M D 0&M D D 00&+$L,+M D D &)(&+1M D D ,+ C 0 .0L&,+M &1.0,.,0L&,+L&,+M+0 L&,+1,#L5,1 *&G* L#,0*1,#% * 07L%0&+D$$$$ DLKCM&%'MQXOSGQXURD LNXY

(275) D D ,0*&(M D D *M D D ,),*,+C % *&) + 1. L0,1,.& 1LK& 1 ,# L% *&6 G4) +L 0&4L&4 1,#L% +,+G% * &0,+.0,L &+% * 07L%0&+D$$$$DLLDM &&(MSRPPGSRTSD LNSY D +M D ,+ LM D 0 LM D 0+0M D ( 0M

(276) D K$& 0M 8D ,K11 (1,KM D %0,+G,)LM

(277) DGD L,K0C 8 *, ) ,# 1 *&* L % * 07L%0&+B 1. L0,1,.& 4& + ,#4) + ),)&8L&,+&+&1J\G0,67)L,KJ\G.% +,)L,K&&0,+J M K,*.) 6 1&+ 1,)KL&,+D!$$#$$$DLLHM()MUXXGUSRD LQRY D 0+0M D ,+ LM

(278) D K$& 0M D %0,+G,)LM 8D 0,+8& 0M

(279) DGD K%$K 1M

(280) DGD L,K0C8*&6 G4) +L J K J K,*.) 65&L%+K+17** L0&)L 0*&+).% +,6,)&$+ 1*, )#,0L% L&4 1&L ,#.K0.) &.%,1.%L1 1D!$$#$$$DLLGM ((MXXTGXXSD NX.

(281) . LQNY D 84 +& 0M D K,&1M D K,K0 K6M

(282) DGD L,K0C 8 &&0,+ ,*.) 6 * &L 1 + &+L0*,) K)0 )&.%L& %70,67)L&,+ 7 40&,K1 ,67$ + ,+,01D $ $ ECCHM OXRGOXQD LQQY D 84 +& 0M D K,&1M

(283) DGD L,K0C +L 0*,) K)0 0,*L& %70,67)L&,+ * &L 7 &+K) 0 &0,+ ,*.) 6C + ,6,G L&4 &+L 0* &L &1 1K$$ 1L D !$ $ $ ECCGM',MTXQGTXOD LQJY D 84 +& 0M

(284) DGD L,K0C L)7L& 8&0&&+L&,+ ,# ,) #&+1 + *&L&,+ ,# L%&,+&1,) 7 +,+G% * &0,+,*.) 6D$$ECCGMNUOOGNUOUD LQOY D84 +& 0MD ,K0"MDK,K0 K6MD"+!/K M

(285) DGD,KM

(286) D"KLMD%0,+G,)LM 8D 0,+8& 0M

(287) DGD L,K0C K)L&.) 80,*L& 8*&+L&,+ &L 7 &&0,+ ,*.) 6D !$$$$ECCKM)+MTNUGTNTD LQUY D ,K0"M D%&KMD0,+&MD ,+MDK,K0 K6MD 0&G 00 1MD)"*+ 7M

(288) DGD ,KM 8D D ,&+M D

(289) /K* LM D K,&1M D ),+&+M

(290) DGD L,K0C 4 01&) J K.0,L,+L&,+G +K ) + +4 01&,+ &+ &6 G) +L &&0,+J M K ,*.) 6 1D $ $ECDDM*%MPORXGPONRD LQPY D8D 7%0LMD

(291) D 7 0C. G&+K &+L0*,) K)0 ) L0,+L0+1# 0D$$DLKIM '*MOXRTGOXRXD LQTY

(292) D D ,. 0M

(293) D D 7 0C ),5 %70,$ + L,* 1 )#G 6%+$ L5 + 1J K +&)& + 1J K +&)&+ ,*.) 6 1C )L&,+1%&.1 5&L% ) L0,+ + .0,L,+ L0+1# 0 1 )#G 6%+$ D $ $$$ECCFM&'*MNQQNTGNQQQSD . NS.

(294)

(295) . . . 8_. . 8,(.('D(/*%%.,('.,'-,= "-(0,3(.!*!'(&' .

(296) . .

(297)

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``S; - " " +; .1( "--3&&.,"%" '-,'('((,"'."' ,(/*F]D''E'%QGFTG> . .

(299) . . . . . . . . . . . ,)D8D8')*$++ %$%+" $*) -)%# '#'==>N E0>. +=>+)# $"'$%" =N< %)<$ >$=>$%$%%) $+ $)%,'*=N;$%)<$"E>8. . . . QR.

(300)

(301) "0. . "' D' ,(/*"'.,(/."('(-'(.-./,..!((,"'."('(('",('(.!*",;. .! (,,-*('"' &"2 0%'. (&*%2 *(----- ((,"'. -(%0'. &(%/% F1., "' ,3-.%-G> !- &(""."('- ! -,0 - ('."'/."(' "' .! *,*,."(' ( "--3&&.,"% "",('F. ;. G (&*%2-; 1!"! &"&" .! ((,"'."(' ( .! .3,(-"'. . .! 8 ."0 -".FQG> % _>_ %"-.- .! (&*%2- ,*(,. "' .! %".,./, -3'.!-"4 1".! .! %" '- -!(1' "' " /,_>_> "D8D8

(302) *+%+ )%$%#'"/*% $+)*+)'%)+ $+" +)+,)8. (&*%2. !&"%(,&/%. >. D3. D. HF*&*GQFaD,GQIQ\. FU;VG. -. D. HF*&*GQFaD8GQIQ\. FWG. E. HF D'GQFaD8GQI\. FS;XG. E. HF D'GQFaDQF!GQGQI\. FRG. . . F. HF D'GQFaQD&**GF QGIQ\. F_G. . -. F9. HF D'GQFaQD&**GF RGIQ\. FTG. . . F. HF D'%QGQFaQD&**GF R GIQ\. FTG. . -. F9. HF D'%QGQFaQD&**GF RGIQ\. FTG. . . G. HF D!GQFaQD&**GI\. FRG. . -. . . . -. . ! "."('% ," "' %" '- , ".!, .1( "'."% ,(23%.- F.. ] 8E;. *,(*"('. ] ,EG (, *!(-*!.- F"*!'3%*!(-*!. ] F!GQQEG (, "-D,(23%. FD *!'3%'"*,(*"('.]&**QEG>!3,,1'"'" /,_>Q> . . . . . . . . . . . . . . . ,)D8E8/+)) * $+ )%$%#'"/*" *+ $"D8D7>++6>')%' %$+6> ; '$0"$ ')%' %$+6> '$0"'%*'+8. QS.

(303)