FROM IRON(II) TO IRON(III) BASKET HANDLE PORPHYRINS : STATIC AND KINETICS X-RAY ABSORPTION STUDIES

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FROM IRON(II) TO IRON(III) BASKET HANDLE PORPHYRINS : STATIC AND KINETICS X-RAY

ABSORPTION STUDIES

M. Verdaguer, C. Cartier, M. Momenteau, E. Dartyge, A. Fontaine, G.

Tourillon, A. Michalowicz

To cite this version:

M. Verdaguer, C. Cartier, M. Momenteau, E. Dartyge, A. Fontaine, et al.. FROM IRON(II) TO IRON(III) BASKET HANDLE PORPHYRINS : STATIC AND KINETICS X-RAY AB- SORPTION STUDIES. Journal de Physique Colloques, 1986, 47 (C8), pp.C8-649-C8-652.

�10.1051/jphyscol:19868123�. �jpa-00226022�

C o l l o q u e C8, s u p p l e m e n t a u n o

FROM IRON(I1) TO IRON(II1) BASKET HANDLE PORPHYRINS : STATIC AND KINETICS X-RAY ABSORPTION STUDIES

M. VERDAGUER* , * * , C. CARTIER* , M. MOMENTEAU* * " , E. DARTYGE' ,

A. FONTAINE*, G. TOURILLONt a n d A. MICHALOWICZ+,++

" ~ a b o r a t o i r e SET, Universite de Paris-Sud, Bgtiment 420, F-91405 Orsay Cedex, France

* * Ecole Normale Superieure, Le Parc, F-92211 Saint-Cloud, France

* * t

Institut Curie, Section Biologic, Universite de Paris-Sud, Bdtiment 112, F-91405 Orsay Cedex, France

'LURE, (CNRS, CEA, MEN), Universite de Paris-Sud, Bgtiment 209 D , F-91405 Orsay Cedex, France

"Laboratoire d e Physico-Chimie Structurale, Universite de Creteil, F-94000 Creteil, France

RESUME

Lea p o r p h y r i n e s d e fer h a n s e s d e p a n i e r p r e s e n t e n t des genes s t e r i q u e s a u r l e a d e w faces d u cycle porphyrinique e t une grande stabilite par r a p p o r t h l ' o x y d a t i o n par l e dioxygene

.

p l a n car*; Im-Fe( I1 )-Q2, o c t e d r i q u e ; Fe( 111 )-OH, p y r d d e h base c a r r e e l , e n s o l u t i o n o u h l ' B t a t s o l i d e , pour mieux c o n n a i t r e s t r u c t u r e m o l e c u l a i r e e t f o n c t i o n d e ces a n a l o g u e s d'hemee f i x a n t l'oxyg@ne.Nous p r e s e n t o n s egalement les ~ ~ 8 u l t a t S p n S l i m i n a i r e s d e 1'Btude c i n e t i q u e par EXAPS rBeolu d a n s l e tempa,de l ' o x y d a t i o n p a r lloxyg@ne m o l e c u l a i r e d ' u n e p o r p h y r i n e d e F e ( I 1 ) h a n s e de p a n i e r (B H P ) , e n d e r i v e BHP- Fe( I11 )-OH.

A B m R F c r s

The 8o-calledironba~kethandleporphyrinspresentsteriChindran~Onboth faces o n t h e porphyrinringandalargestabilitytowardsoxidationbydioxygen.Weareinvestigatinga series o f such compounds [Square p l a n a r Pe( I1 ) , o c t a h e d r a l Im-Fe( I1 )-02, and s q u a r e pyramidal l l e ( I I I ) - O H I , i n s o l u t i o n o r i n s o l i d state, to g e t new i n s i g h t s i n t o t h e m o l e c u l a r s t r u c t u r e a n d f ~ n c t i o n o f t h e s e a n a l o g s o f 0 ~ b i n d i n g h e m e p r o t e i n s . F i n a l l y , w e presentpreliminaryresults usingdispersivemodeEXZWS, about t h e r e a c t i o n o f o x i d a t i o n o f F e ( I 1 ) b a s k e t h a n d l e p o r p h y r i n s (B H P ) by dioxygen, towards t h e f o r m a t i o n o f BHP- Fe( 111 )-OH compound.

I n e o l u t i o n , a u t o x i d a t i o n o f f l a t - o p e n porphyrin-iron ( 1 1 ) complexes which i n v o l v e s an e x t r e m e l y r a p i d b i m o l e c u l a r r e a c t i o n g i v e s f i n a l l y a p-oxodimer when t h e y are exposed to d i o x y g e n ( l , 2 ) . T h i s r e a c t i o n d o e s n o t o c c u r i n hemoproteins (hemoglobin, myoglobin) becausetheproteinchainsurroundingthehemepreventsthecloseapproachofthetvohemes and t h e subsequent o x i d a t i o n .

B-PFe( I1 )

+

B-PFe( 11 )+

+

+~-pFe(Iv)?) ---B P F e ( I I I ) + P F e ( I I I ) I r r e v e r s i b l e a u t o x i d a t i o n . To i n h i b i t such a n u n d e s i r a b l e r e a c t i o n s e v e r a l s u p e r s t r u c t u r e d p o r p h y r i n s have been proposed( 3 )

.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19868123

C8-650 JOURNAL DE PHYSIQUE

which have been c h a r a c t e r i z e d by U.V.-visible, EPR and N M R s p e c t r o s c o p i e s ( 5 ) and by e l e c t r o c h a n i s t r y ( 6 ) . O n t h e o t h e r h a n d , t h e p r e s e n c e o f a n a p p e n d e d n i t r o g e n d o n o r l i g a n d ( p y r i d i n e , imidazole ) i n one o f the two h a n d l e s allowed t o o b t a i n pure f i v e coordinated

-

i r o n ( I1 ) complexes ( s 2 ^), as i n the deoxyform of dioxygen carrier hemoproteins. They r e v e r s i b l y b i n d dioxygen at nxm temperature and provide s y n t h e t i c nrcdel ^systems t o analyae the f a c t o r s c o n t r o l l i n g t h e dioxygen a f f i n i t y and the exact e l e c t r o n i c n a t u r e of stable dioxygen adduct ^(S=O) i n n a t u r a l compounds(7 ) , Such complexes can be also obtained from s i n g l e f a c e hindered compounds b e a r i n g one handle and two pivalamido p i c k e t s i n the presence of free nitrogenous base i n s o l u t i o n ( 6 ) .

W e p r e s e n t i n t h i s corcwunication the i n v e s t i g a t i o n o f EXAPS and ^XANES d a t e o f ^BHP Fe( I1 ),

Fe( I1 )-OZ and Fe( I11 )-OH ~ o m p l e ~ e s o f basket-handle porphyrins ( F i g u r e 1 )

.

of s t r u c t u r a l d a t a for the hematine d e r i v a t e a r e compared _{t o} t h o s e o f analogous chlorohemin CFe( 111 ) - C l I determined by X-Ray d i f f r a c t i o n ( 9 ) . The XANES s p e c t r a o f the d i f f e r e n t s p e c i e s i s s u f f i c i e n t l y d i f f e r e n t t o a l l o w k i n e t i c s r e s u l t s about the r e a c t i o n of o x i d a t i o n o f four-coordinated F e ( I 1 ) complexes by dioxygen, towards the formation o f Fe( III)-OH s p e c i e s , u s i n g d i s p e r s i v e mode KXWS (10).

X: OH-

EXPERIMENTAL CONDITIONS

C l a s s i c a l ^{XANES and} EXAPS d a t a w e r e recorded at LURE on EXAFS I spectrometer u s i n g a channel c u t S i 400 monochromator, and KXWS 111 (double crystal S i 311). The r i n g s t o r a g e energy was 1.72 GeV. A 8 jm Fe m e t a l l i c f o i l Spe~tIWa was recorded just before each XANES experimental spectyum.

Time r e s o l v e d XANES d a t a w e r e recorded on t h e d i s p e r s i v e X- R a y a b s o r p t i o n facility ( l o ) , u s i n g a Bw-Fe( 11 ) s o l u t i o n i n t o l u e n e (0.05 M), i n a 1 ern cell w i t h kapton windows, under gaseous oxygen f l o u and s t i r r i n g . Accumulation time was 10s per spectrum.

XANES

-

.

P e ( I 1 ) comwunds t The i n t e n s e W e l l d e f i n e d t r a n s i t i o n observed at 7112.6 eV is characteristic of the s q u a r e p l a n a r P e ( I I ) ( S = l ) i n p o r p h y r i n i c surroundings. F o r coapounds&and 2, t h e r e i s n o s h o ~ l d e r i n t h e e d g e . Preedge features(weakintensityeven i n the o c t a h e d r a l Fe( I1 )-02, Im) lies at low energy ^{( 7108.0} e V for Pe( ^I1 ), 7108.2 ev for P e ( I 1 )-02, Im)

.

Fe(II1)-X s q u a r e pyramidal romplext?~ z F o r all t h e compounds, w e observe a n unresolved s h o u l d e r i n t h e edge, the energy of which is X dependent. ^A possible a t t r i b u t i o n should be

an allowed charge t r a n s f e r t x 4 F e . As expected, preedge f e a t u r e s lies at h i g h e r energy t h a n i n i r o n ( I 1 ) and the C s q u a r e pyramidal ] i n t e n s i t y of the d i p o l a r allowed t r a n s i t i o n s i n c r e a s e s w i t h d i s t o r t i o n f r o m e q u a r e p l a n ~ t o s q u ~ p y r a m i d a l C l a r g e r p a r t i c i p a t i o n o f 4p(Fe) atomic o r b i t a l s i n t h e molecular o r b i t a l c o n t a i n i n g t h e 3d(Fe)l

.

m s

W e use the classical plane wave EXAFS a n a l y s i s described else where ( l l ) , W e study two compounds : the BHP-Fe( 111 )+I s p e c i e s with a known c r y s t a l l o g r a p h i c s t r u c t u r e ^{( 9 )} and the rare BHP-Fe( I11 )-OH where no s t r u c t u r a l d a t a are a v a i l a b l e . For the two first shells, r e s u l t s are obtained by a two s h e l l s f i t t i n g procedure, with ^Tea and Lee phase s h i f t s and amplitudes. Distances Fe-C and F,- are obtained using Ben1 and Lee c r i t e r i o n , w i t h a phase c o r r e c t i o n on t h e first neighbour s h e l l . The r e s u l t s are i n Table I. The proposed

~ t r u c t u r e for t h e hydroxo s p e c i e s is schematized i n Fig. ³

.

Ze-0

ligand ( 1 2 )

.

COllWUND Boll0 DlSTArCES DEBYE YALLER

'

W A 2312

X.R.D. E.X.A.F.S.

F a 4 2.06 2.06 0.W32 ^I L:

FE 4 HIDROXO SPECIES

8HP F E ( I I I I - U H

F ~ - c & s o

Figure 3: proposed s t r u c t u r e f o r BHP-F~(III)-OH.

TIME RESOLVED XANES : K i n e t i c s o f oxidation.

1/2 o*.E+

--Fe( 11 ) ---+ BHp-~e( 111 )-OH Square p l a n a r Square pyramidal

C8-652 JOURNAL DE PHYSIQUE

Fig.4 shows experimental spectra o f t h e Pe( 11 ) square p l a n a r complex A, b e f o r e t h e o x i d a t i o n . During t h e r e a c t i o n , we observe t h e disappearance o f t h e F e ( I 1 ) square p l a n a r c h a r a c t e r i s t i c f e a t u r e a t 7112,6 eV. The e v o l u t i o n o f t h e r e l a t i v e i n t e n s i t y o f t h i s peak is g i v e n i n F i g . 5

.

~rudentgiventhelwsignal/noiseratioduetothephotonstatistics(~rkintoodilute s o l u t i o n and t o o s h o r t time of accumulation). A s t u d y o f a slower o x i d a t i o n r e a c t i o n with

more concentrated s o l u t i o n s (more s o l u b l e BHP) would be necessary t o g i v e q u a n t i t a t i v e conclu8ions. Nevertheless, t h e s e preliminary r e s u l t s confirm t h e power o f time reeolved X-Ray absorption i n t h e emergence o f a new t o o l f o r r e a c t i v i t y s t u d i e s : s t r u c t u r a l k i n e t i c s .

Figure 4: XANES s p e c t r a f o r t h e Fe( 11 ) square p l a n a r complex.

Figure 5: Evolution o f t h e r e l a t i v e i n t e n s i t y o f t h e peak a t 7112.6 eV.

CONCLUS1oNs

Eesides t h e fundamental i n t e r p r e t a t i o n o f XANES s p e c t r a o f Fe( I1 ) o r Fe( 111 ) BIIP, which is d i f f i c u l t ( m i x i n g o f states, m u l t i p l e t s

...

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