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Tris(diethylthiophosphato)aluminum(III)
INORG.NUCL.CHEM.LETTERS VoI.17, No.5/6, pp.195-199, 1 9 8 1 . Printed in Great Britain.
TRI8 (DIETH YLTHIOPHOSPHATO )A L ~ I ~
0020-1650/81/060195-05502.00/0 Pergamon Press Ltd.
(III )
Chester M.Mikulski, Suneet Chauban, Richard Rabin Department of Chemistry&Physics, Beaver College, Glenside, PA 19038; U.S.A. and N i c h o l a s M.Karayannie
Amoco Chemicals Corporation, Naperville, IL 60566; U.S.A.
(Received 24 February 1981) Previous synthetic studies at these laboratories reactions
o f an e x c e s s o f n e a t t r i e t h y l -
established
that during
or t r i - n - b u t y l - t h i o p h o s p h a t e
( t e t p and
tbtp, respectively; (RO)3F--S) with a wide variety of metal chlorides (M = Fe2÷, gO2+ Ti3+, V 3+, Cr3÷, Fe3+ y3+ lanthanide(III), Th ~ , g 4+) at elevated temperatures (I(X)-220°C.), polymeric (MLn)x (n = 2, 3 or 4) ccaplexes with the diethyl- or di-n-butyl-thlophosphato llgand (detp or dbtp, respectively; (RO)2POS') are easily precipitated (I-3). However, in the corresponding reactions of the same neutral th~ophosphate esters with AICI3, MCI 2 (M = Mn, Co, Ni, Zn) or MI (M = Li, Na, K, Rb, Cs), the initially formed M(detp) n or M(dbtp) n complexes are attacked by the HX (X = Cl or I) by-product of the reaction, and the resulting products undergo condensation reactions, yielding H2S and metal complexes with pyrothiophosphato ligands (i.e., (O2P(OR)-S-(RO)PO2)2-, where R = C2H5, n-C4H9, or (O2P(O)-S-(O)PO2)4-) as final products (4). Thus, reaction of AICI3 with tbtp led to the precipitation of AI2(O2P(O-n-C4H9)-S-(n-C4HgO)PO2)3°xH20,_ while, during the corresponding reaction with tetp, an A13+ pyrothiophosphato complex, not sufficiently pure for characterization, was isolated (4). On the other hand, synthetic studies of tetp adducts with metal perchlorates, with triethyl orthoformats as preparation medium, revealed that authentic tetp adducts with A13+, Cr3+, Fe3+, Co2+, Zn2+, Cd2+, Hg 2+ and AE + perchlorates can he isolated (5); nevertheless, the interaction of tetp with Ni2+ and Cu2+ perchlorates, under similar conditions, led to the precipitation of ~ t p complexes of the types Ni(detp)(CiO4).3H20 and Cu2(detp)(CiO4)3-4H20 (5,6). The latter two products are believed to a r i l l psrchlorate-tetp
froo thermal decooposition of the initially formed metal
a d d u c t a , a s follows (5,6):
195
196
Tris(diethylthiophosphato)aluminum(lll)
Ni(tetP)n(Cl04)2 ~ 2Cu(tetP)n(CIO4)2 ~
Ni(detp)(CiO4) + (n-1)tetp + C2H5OCIO3
(1)
Cu2(detp)(CiO4)3 + (2n-1)tetp + C2H5OCIO3
(2..)
A s i m i l a r r e a c t i o n between AgNO3 and t e t p was found t o l e a d t o formation o f Ag(detp) and e t h y l n i t r a t e ( 7 , 8 ) .
The e t h y l p e r c h l o r a t e by-product o f r e a c t i o n s
(I..) and (2..) i s somewhat uncommon; however, a l k y l p e r c h l o r a t e s have been r e p o r t e d l y o b t a i n e d and i d e n t i f i e d during r e a c t i o n s o f AgCIO4 with a l k y l h a l i d e a (9) or a l c o h o l s with anhydrous HCIO4 (10). Reactions o f types (1) and ~2) a r e analogous to those p o s t u l a t e d f o r the formation o f M(detp) n complexes by r e a c t i o n o f t e t p with metal c h l o r i d e s , v i z .
(1-3,11-1)) : M(tetP)nC1 n ~
M(detp) n + nC2HsC1
(3)
A l i k e l y d i f f e r e n c e between (1) or (2..) and (3) might be t h a t , whereas the C2H5C1 formed i n (3) p a r t i a l l y decompoles t o y i e l d CH2=CH2 and HC1 ( r e a c t i o n c a t a l y z e d by the metal c h l o r i d e complex p r e s e n t ( 1 4 , 1 5 ) ) , formed i n (1) and (2) would probably remain i n t a c t .
the e t h y l p e r c h l o r a t e
I t was, t h e r e f o r e , f e l t
t h a t the M(detp) n complexes t h a t could not be obtained by r e a c t i o n of t e t p with
metal halidee (M : Li+, Na+, K+, RB+, Cs+, A13+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, etc.), owing to attack of the detp ligands by the hydrogen halide by-product of the r e a c t i o n ( 4 ) , might be easy t o s y n t h e s i z e by r e a c t i n g t e t p with the c o r r e s ponding metal p e r c h l o r a t e s .
Accordingly, r e s e a r c h i n t h i s d i r e c t i o n was i n i t i -
a t e d , and the s y n t h e s i s o f Al(detp) 3 was indeed accomplished and i s h e r e i n r e ported al o n e with p e r t i n e n t IR c h a r a c t e r i z a t i o n d a t a .
This complex can be ob-
t a i n e d e i t h e r by r e a c t i o n of AI(CI04) 3 with neat t e t p or by h e a t i h g s o l u t i o n s o f l i g a n d and s a l t i n t r i e t h y l o r t h o f o r m a t e ; the former p r e p a r a t i v e method w i l l be d e s c r i b e d i n t h i s l e t t e r . Hydrated AI(CI04) 3 was d i s s o l v e d i n a l a r g e excess o f t e t p a t ambient tomp e r a t u r e , and the temperature o f the r e s u l t a n t s o l u t i o n was imcreased by 1-2°C. per min ( t h e n e c e s s a r y p r e c a u t i o n s were taken, i n view of the e x p l o s i o n h a z a r d ) . Al(detp) 3 s t a r t e d p r e c i p i t a t i n g a t ca. 75°C., and the p r e c i p i t a t i o n was complet e ( y i e l d o f 9 ~ o f the t h e o r e t i c a l ) at 8~-90°C.
The•,
the mixture was allowed
t o c o o l , the supernatant was removed, and the white s o l i d complex waus washed with anhydrous d i e t h y l e t h e r and s t o r e d i n v.acuo over anhydroas C-sO4.
found(malcd.)% for C1~3oO~3S3AI:
Analysis,
C 27.11(26.97); H 5.?2(5.66); P 17.O8(17.39);
Tris(diethylthiophosphato)alumi~um(lll)
]97
S 17.75(18.00); A1 4.83(5.05); C1 O.13(O.00). The new coaplex is a i"r - and moisture-stable and i n s o l u b l e i n w a t e r and a l l c ~ o n spectrum i s t y p i c a l
organic solvents.
I t s IR
f o r M(detp) n c o a p l e x s s ( 3 , 1 6 ) ; main IR bands, w i t h a s s i g n -
ments in parentheses (1-6,16-22), CR'I: 121OTs~p_O) , 1111vS(~c_o_(p)) , 103Ovs
(~P-O-(C))' 951ms(C2H5 rocking), 817w,sh(~p_8), 788ms(~p_O_(C )), 712w(CH2 rocking), 5 9 ~ S ( ~ p . S ) .
The absence o f ~P-O a b s o r p t i o n above 1215 ca -1 o r ~P-S ab-
s o r p t i o n a t ca. 620 cm"1 i n d i c a t e s
t h a t both t h e oxygen and s u l f u r s i t e s
POS fragment o f t h e d e t p l i g a n d s a r e c o o r d i n a t e d t o A13÷ ( 1 - 3 , 1 6 , 2 0 - 2 2 ) . t h e most l i k e l y s t r u c t u r a l
alkoxy, aryl,
gahd b r i d g e s ,
viz°
Hence,
type o f t h e o b v i o u s l y p o l y m e r i c new complex would be
analogous to those established (R = a l k y l ,
of the
f o r M3+ complexes w i t h R2POO- o r R2PC~- l i g a n d s
etc.),
i.e.,
linear
chainlike,
involving triple
li-
~AI-(O-P(OC2Hs)2-S>~x , with the detp ligands functioning
as e x c l u s i v e l y b i d e n t a t e b r i d g i n g , O,S-bonded ( 1 - 3 , 2 3 - 2 5 ) °
I t should be noted
a t t h i s p o i n t t h a t t h e IR spectrmm o f t h e new complex does not show bands a t t r i butable to the presence of either
w a t e r o r t h e p e r c h l o r a t e group, as e x p e c t e d .
Research c u r r e n t l y underway i n d i c a t e s t h a t many M(detp) n complexes can be p r e p a r e d by r e a c t i n g t e t p w i t h m e t a l p e r c h l o r a t e s . p l e x e s i s complete a t 75-130°C°
Precipitation
o f t h e s e com-
P r i o r t o c o n c l u d i n g , i t s h o u l d be n o t e d t h a t ,
i n a d d i t i o n t o t h e methods o f p r e p a r a t i o n o f m e t a l d i a l k y l t h i o p h o s p h a t e a by r e a ctimg trialkyl temperatures
t h i o p h o s p h a t e s w i t h MXn (X = C1, Br, I , NO3, C104) a t e l e v a t e d (1-3,5-8),
t h e f o l l o w i n g p r o c e d u r e s have been a l s o employed:
a c t i o n o f sodium o r ammonium d i a l k y l te metal salt
or diaryl-thiophosphate
Inter-
w i t h an a p p r o p r i a -
(M = Ca2+, Ba 2÷, Co2+, Cu2÷, Zn2+, Pb 2+) ( 2 0 , 2 1 , 2 6 ) ;
and r e a c t i o n
o f a d i a l k y l phomphite w i t h a m e t a l o x i d e o r c a r b o n a t e (M = Zn2+, Cd2+) and p u l v e r u l e n t s u l f u r i n an o r g a n i c s o l v e n t ( a l c o h o l , t o l u e n e )
(27).
REFERENCES 1. C.M.Mikulski, M.M.Karayannie and L . L . P y t l e w s k i ,
Inorg.Nucl.Chen.Lett.,Z,785
(1971). 2. C.M.Mikulski, L.L.Pytlewakl mad N.M.Kar~Tannis, J.Leea-Co|mon Metals,~,3Y?
(1973). 3- C.M.Mikulski, L.L.Pytlewski and N.M.Karayannla, J.Inorg.Nucl.Chea.,~_~,2411 (1975) •
Tris(diethylthiophosphato)aluminum(lll)
198
4. C.M.Mikulskl, L.L°Pytlawskl and N.M.Karayannis, Inorg.Chem.,1_~4,1559(1975). 5- C.M.Mik~leki, S.Chauhan, R.Rabin and N.M.Karayannis, Abstracts, the 2nd Chem.Congress of North Amer.Continent, Las Vegas, Nevada, AuI.2~-29,1980! No. INOR 21;
Idem., J.Inorg.Nucl.Chem.,in press.
6. C.M.Mikulski, L.L.Pytlewski and N.M.Karayannis, Inorg.Chlm.Acta,2.22,LT(1977). 7. H.Tsichmann and G.Hilgetq, Angew.Chem.,79,1077(1967) • 8. G.Hilgetag, K.-H.Schwarz, H.Teichmann and G.Lehmann, Chem.Ber.,93,2687(1960). 9- H.Burton and P.F.G°Prail, Chem.lnd.(London),939(1951); H.Burton, D.A.Munday and P.F.G.Prail, J.Chem.Soc.,3933(1956); A.Gandini and P.H.Plesch, J.Polym.
Sci. ,B_,~, la?(1965) • 10. A.A.Zinov'ev, l.A.Zakharova and G.P.Kondratskaya, Zh.Neorg.Khim.,~,2390(195~). 11. N.M.Karayannis, C.N,Mikulski and L.L.Pytlewski, Inorg.Chim.Acta Rev.,~,69
(1971). 12. V.Gutmann and K.Fenk-rt, Monatsh.Chem.,99,14~(1968); V.Gutmann and G.Beer, InorE. Chlm.Acta,~, 87( 1969). I). C.M.Mikulekl, N.M.Karayannls, J.V.Minkiewicz, L.L.Pytlewekl and M.M.Labee, I n o r g . C h i l .Ac t a , ~ , ~ 3 ( 1 9 6 9 ) •
14. H. Noller and K.Ostermeier, Z.Elektrochem.,6_~,191(1959). 15. G.Ya.Kabo and D.N.Andreevlkii, Neftekhimiya,~,76/+(196)).
16. J.a.Pitts, M.A.Robinson and S.I.Trotz, J.Inorg.Nucl.Chem. ,30,1299(1968) ; 31,
3685( 1969). 17. L.C.Thomas and R.A.Chittendsn, Spectrochim.Acta,20,467,~9(1964) ; 21,19o5 (1965); 26A,781(1970). 18. R.A.Chittendsn and L . C . ~ ,
Spectrochim.Acta,20,1679(1964).
19. C.M.Nikulski, W.Henry, L.L.Pytlewski and N.M.Karayannls, Transition Met.Chem., 2,1)5( 1977). 20. M.I.Kabachnik, T.A.Mastryukova, E.I.Matrosov and B.Flsher,
Zh.Strukt.Khim.,
6, 691 (1965) • 21. S.V.Larionov and L°A.II'ina, 2~.Obshch.Khil.,~,~(196~). a2. A.F.Valil'ev and B.A.Khaskin, Zh.Obshch.Khlm.,~,2~2(1964).
2). L.S.Siith, P.R.Newaan, A.J.Heeger, A.F.Gltrito, H.D.GI11 ,~,* and P.Nannelli, J. CheI.Phys.,66,5428(19"/7); R.Cini, P.Orioli, H.D.Gillman and P.Nannelli, Cryst. S t r u c t . Camlun. ,8,621 (1979) •
Tris(diethylthiophosphato)aluminum(lll)
24. S.Bruckner, M.Calligaris, G.Nardin, L.Randaccio and A.Ripamonti, Chem.Commun., 474(1969); M.Calligaris, A.Ciana, S.Meriani, G.Nardin, L.Randaccio and A. Ripamonti, J.Chem.Soc. ,A,3386(19"70). 25. E.E.Flagg and D.L.Bchmidt, J.Am.Chem.Soc.,90,4173(1968). 26. V.G.Pesin and A.M.Khaletskii, Zh.Obshch.Kk~m. ,31,2508(1961). 27. B.Lippsmeier(to Hoechst Aktienges.), British Pat.Specif., 1,473,010(11 May 1977).
199
TRI8 (DIETH YLTHIOPHOSPHATO )A L ~ I ~
0020-1650/81/060195-05502.00/0 Pergamon Press Ltd.
(III )
Chester M.Mikulski, Suneet Chauban, Richard Rabin Department of Chemistry&Physics, Beaver College, Glenside, PA 19038; U.S.A. and N i c h o l a s M.Karayannie
Amoco Chemicals Corporation, Naperville, IL 60566; U.S.A.
(Received 24 February 1981) Previous synthetic studies at these laboratories reactions
o f an e x c e s s o f n e a t t r i e t h y l -
established
that during
or t r i - n - b u t y l - t h i o p h o s p h a t e
( t e t p and
tbtp, respectively; (RO)3F--S) with a wide variety of metal chlorides (M = Fe2÷, gO2+ Ti3+, V 3+, Cr3÷, Fe3+ y3+ lanthanide(III), Th ~ , g 4+) at elevated temperatures (I(X)-220°C.), polymeric (MLn)x (n = 2, 3 or 4) ccaplexes with the diethyl- or di-n-butyl-thlophosphato llgand (detp or dbtp, respectively; (RO)2POS') are easily precipitated (I-3). However, in the corresponding reactions of the same neutral th~ophosphate esters with AICI3, MCI 2 (M = Mn, Co, Ni, Zn) or MI (M = Li, Na, K, Rb, Cs), the initially formed M(detp) n or M(dbtp) n complexes are attacked by the HX (X = Cl or I) by-product of the reaction, and the resulting products undergo condensation reactions, yielding H2S and metal complexes with pyrothiophosphato ligands (i.e., (O2P(OR)-S-(RO)PO2)2-, where R = C2H5, n-C4H9, or (O2P(O)-S-(O)PO2)4-) as final products (4). Thus, reaction of AICI3 with tbtp led to the precipitation of AI2(O2P(O-n-C4H9)-S-(n-C4HgO)PO2)3°xH20,_ while, during the corresponding reaction with tetp, an A13+ pyrothiophosphato complex, not sufficiently pure for characterization, was isolated (4). On the other hand, synthetic studies of tetp adducts with metal perchlorates, with triethyl orthoformats as preparation medium, revealed that authentic tetp adducts with A13+, Cr3+, Fe3+, Co2+, Zn2+, Cd2+, Hg 2+ and AE + perchlorates can he isolated (5); nevertheless, the interaction of tetp with Ni2+ and Cu2+ perchlorates, under similar conditions, led to the precipitation of ~ t p complexes of the types Ni(detp)(CiO4).3H20 and Cu2(detp)(CiO4)3-4H20 (5,6). The latter two products are believed to a r i l l psrchlorate-tetp
froo thermal decooposition of the initially formed metal
a d d u c t a , a s follows (5,6):
195
196
Tris(diethylthiophosphato)aluminum(lll)
Ni(tetP)n(Cl04)2 ~ 2Cu(tetP)n(CIO4)2 ~
Ni(detp)(CiO4) + (n-1)tetp + C2H5OCIO3
(1)
Cu2(detp)(CiO4)3 + (2n-1)tetp + C2H5OCIO3
(2..)
A s i m i l a r r e a c t i o n between AgNO3 and t e t p was found t o l e a d t o formation o f Ag(detp) and e t h y l n i t r a t e ( 7 , 8 ) .
The e t h y l p e r c h l o r a t e by-product o f r e a c t i o n s
(I..) and (2..) i s somewhat uncommon; however, a l k y l p e r c h l o r a t e s have been r e p o r t e d l y o b t a i n e d and i d e n t i f i e d during r e a c t i o n s o f AgCIO4 with a l k y l h a l i d e a (9) or a l c o h o l s with anhydrous HCIO4 (10). Reactions o f types (1) and ~2) a r e analogous to those p o s t u l a t e d f o r the formation o f M(detp) n complexes by r e a c t i o n o f t e t p with metal c h l o r i d e s , v i z .
(1-3,11-1)) : M(tetP)nC1 n ~
M(detp) n + nC2HsC1
(3)
A l i k e l y d i f f e r e n c e between (1) or (2..) and (3) might be t h a t , whereas the C2H5C1 formed i n (3) p a r t i a l l y decompoles t o y i e l d CH2=CH2 and HC1 ( r e a c t i o n c a t a l y z e d by the metal c h l o r i d e complex p r e s e n t ( 1 4 , 1 5 ) ) , formed i n (1) and (2) would probably remain i n t a c t .
the e t h y l p e r c h l o r a t e
I t was, t h e r e f o r e , f e l t
t h a t the M(detp) n complexes t h a t could not be obtained by r e a c t i o n of t e t p with
metal halidee (M : Li+, Na+, K+, RB+, Cs+, A13+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, etc.), owing to attack of the detp ligands by the hydrogen halide by-product of the r e a c t i o n ( 4 ) , might be easy t o s y n t h e s i z e by r e a c t i n g t e t p with the c o r r e s ponding metal p e r c h l o r a t e s .
Accordingly, r e s e a r c h i n t h i s d i r e c t i o n was i n i t i -
a t e d , and the s y n t h e s i s o f Al(detp) 3 was indeed accomplished and i s h e r e i n r e ported al o n e with p e r t i n e n t IR c h a r a c t e r i z a t i o n d a t a .
This complex can be ob-
t a i n e d e i t h e r by r e a c t i o n of AI(CI04) 3 with neat t e t p or by h e a t i h g s o l u t i o n s o f l i g a n d and s a l t i n t r i e t h y l o r t h o f o r m a t e ; the former p r e p a r a t i v e method w i l l be d e s c r i b e d i n t h i s l e t t e r . Hydrated AI(CI04) 3 was d i s s o l v e d i n a l a r g e excess o f t e t p a t ambient tomp e r a t u r e , and the temperature o f the r e s u l t a n t s o l u t i o n was imcreased by 1-2°C. per min ( t h e n e c e s s a r y p r e c a u t i o n s were taken, i n view of the e x p l o s i o n h a z a r d ) . Al(detp) 3 s t a r t e d p r e c i p i t a t i n g a t ca. 75°C., and the p r e c i p i t a t i o n was complet e ( y i e l d o f 9 ~ o f the t h e o r e t i c a l ) at 8~-90°C.
The•,
the mixture was allowed
t o c o o l , the supernatant was removed, and the white s o l i d complex waus washed with anhydrous d i e t h y l e t h e r and s t o r e d i n v.acuo over anhydroas C-sO4.
found(malcd.)% for C1~3oO~3S3AI:
Analysis,
C 27.11(26.97); H 5.?2(5.66); P 17.O8(17.39);
Tris(diethylthiophosphato)alumi~um(lll)
]97
S 17.75(18.00); A1 4.83(5.05); C1 O.13(O.00). The new coaplex is a i"r - and moisture-stable and i n s o l u b l e i n w a t e r and a l l c ~ o n spectrum i s t y p i c a l
organic solvents.
I t s IR
f o r M(detp) n c o a p l e x s s ( 3 , 1 6 ) ; main IR bands, w i t h a s s i g n -
ments in parentheses (1-6,16-22), CR'I: 121OTs~p_O) , 1111vS(~c_o_(p)) , 103Ovs
(~P-O-(C))' 951ms(C2H5 rocking), 817w,sh(~p_8), 788ms(~p_O_(C )), 712w(CH2 rocking), 5 9 ~ S ( ~ p . S ) .
The absence o f ~P-O a b s o r p t i o n above 1215 ca -1 o r ~P-S ab-
s o r p t i o n a t ca. 620 cm"1 i n d i c a t e s
t h a t both t h e oxygen and s u l f u r s i t e s
POS fragment o f t h e d e t p l i g a n d s a r e c o o r d i n a t e d t o A13÷ ( 1 - 3 , 1 6 , 2 0 - 2 2 ) . t h e most l i k e l y s t r u c t u r a l
alkoxy, aryl,
gahd b r i d g e s ,
viz°
Hence,
type o f t h e o b v i o u s l y p o l y m e r i c new complex would be
analogous to those established (R = a l k y l ,
of the
f o r M3+ complexes w i t h R2POO- o r R2PC~- l i g a n d s
etc.),
i.e.,
linear
chainlike,
involving triple
li-
~AI-(O-P(OC2Hs)2-S>~x , with the detp ligands functioning
as e x c l u s i v e l y b i d e n t a t e b r i d g i n g , O,S-bonded ( 1 - 3 , 2 3 - 2 5 ) °
I t should be noted
a t t h i s p o i n t t h a t t h e IR spectrmm o f t h e new complex does not show bands a t t r i butable to the presence of either
w a t e r o r t h e p e r c h l o r a t e group, as e x p e c t e d .
Research c u r r e n t l y underway i n d i c a t e s t h a t many M(detp) n complexes can be p r e p a r e d by r e a c t i n g t e t p w i t h m e t a l p e r c h l o r a t e s . p l e x e s i s complete a t 75-130°C°
Precipitation
o f t h e s e com-
P r i o r t o c o n c l u d i n g , i t s h o u l d be n o t e d t h a t ,
i n a d d i t i o n t o t h e methods o f p r e p a r a t i o n o f m e t a l d i a l k y l t h i o p h o s p h a t e a by r e a ctimg trialkyl temperatures
t h i o p h o s p h a t e s w i t h MXn (X = C1, Br, I , NO3, C104) a t e l e v a t e d (1-3,5-8),
t h e f o l l o w i n g p r o c e d u r e s have been a l s o employed:
a c t i o n o f sodium o r ammonium d i a l k y l te metal salt
or diaryl-thiophosphate
Inter-
w i t h an a p p r o p r i a -
(M = Ca2+, Ba 2÷, Co2+, Cu2÷, Zn2+, Pb 2+) ( 2 0 , 2 1 , 2 6 ) ;
and r e a c t i o n
o f a d i a l k y l phomphite w i t h a m e t a l o x i d e o r c a r b o n a t e (M = Zn2+, Cd2+) and p u l v e r u l e n t s u l f u r i n an o r g a n i c s o l v e n t ( a l c o h o l , t o l u e n e )
(27).
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