5 Chemistry of the Water Gas Shift Reaction Catalyzed by Rhodium Complexes T. Y O S H I D A , T. O K A N O , and SEI O T S U K A
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Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka, Japan 560
Transition metal compounds in various form such as metal carbonyls (1), carbonyl clusters (2), Pt(II) chloride/tin chloride (3), PtL (L=PR ) (4), etc. have been proposed as homogeneous n
3
catalysts for the water gas shift (wgs) reaction (eq. 1).
Some of
them are reportedly active at relatively low temperature ( [Rh(C0)L ] (y-C0 ) 9
2Rh(C0)(0C0 H)L 2
2
2
[Rh(C0)L ] (y-C0 ) + H 0 2
2
3
Rh(C0)(0C0 H)L 2
2
Rh(C0)(0C0 H)L 2
(28)
3
^
2
i s o l a t e solely [Rh(CO)(py)L ]
2
+
+ [Rh(C0)(py)L ]0H
2
(29)
2
but not the bicarbonato compound
from the h y d r o l y s i s , the e q u i l i b r i u m (eq. 30) ap-
2
py> Rh(C0)(0C0 H)L 9
ù
9
ά
-co
?
^
*
co
2
^ [Rh(C0)(py)L ]0H
(30)
9
L
pears to be favored toward the formation of [Rh(CO)(py)L ]0H. 2
t h i s i n f o r m a t i o n we summarize steps a s s o c i a t e d w i t h H (Scheme
2
With
generation
III).
The C a t a l y t i c C y c l e With the i n f o r m a t i o n on the component r e a c t i o n s described above the c o n s t r u c t i o n of the whole c a t a l y t i c c y c l e i s i n order. I t i s h i g h l y u n l i k e l y t h a t the c a t a l y s t precursor RhHL- c a r r i e s the
In Catalytic Activation of Carbon Monoxide; Ford, P.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
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90
CATALYTIC ACTIVATION OF CARBON MONOXIDE
Scheme
III
In Catalytic Activation of Carbon Monoxide; Ford, P.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
5. YOSHIDA ET AL.
Rh-Catalyzed Water Gas Shift
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Scheme IV
H C0 2
r
H0
3
Rh(0C0 H)(C0)U
Rh (p-0 C0)(C0) 2
9
2
2
CO, trans-Rh(0H)(C0)L
H
2
H 0,S
2
2
trans-RhH(C0)L l[trans-Rh(CO)(S)L,]OH Rh(C0 H)(C0)L, 9
CO H,,L
H 0,L 2
Rh (C0) L 2
3
CO
3
In Catalytic Activation of Carbon Monoxide; Ford, P.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
92
CATALYTIC ACTIVATION OF CARBON MONOXIDE
catalytic cycle, as i t readily reacts with CO or H 0, both processes 2
being found low-energy processes. Therefore, RhHLg is not in cluded in the cycle shown in Scheme IV.
All the isolated species
Rh(0H)(C0)L , Rh (C0) L and Rh (y-C0 )(C0) L were tested for the 2
2
3
3
2
3
2
4
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catalysis to confirm their participation in the catalysis (Table I).
Literature Cited 1. King, A. D.; King, R. B.; Yang, D. B., J. Am. Chem. Soc., 1980, 102, 1028-1032 and references cited therein. 2. Ungermann, C.; Landis, V.; Moya, S. Α.; Cohen, H.; Walker, M.; Pearson, R. G.; Rinker, R. G.; Ford, P. C., J. Am. Chem. Soc., 1979, 101, 5922-5929 and references cited therein. 3. Cheng, C. -H.; Eisenberg, R., J . Am. Chem. Soc., 1978, 100, 5968-5970. 4. Yoshida, T.; Ueda, Y.; Otsuka, S., J . Am. Chem. Soc., 1978, 100, 3941-3942. 5. Kassel, L. S., J. Am. Chem. Soc., 1934, 56, 1838-1842. 6. Darensbourg, D. J.; Froelich, J. Α., J. Am. Chem. Soc., 1977, 99, 5940-5946 and references cited therein. 7. Yoshida, T.; Matsuda, T.; Okano, T.; Kitani, T.; Otsuka, S., J. Am. Chem. Soc., 1979, 101, 2027-2038. 8. Bennett, Μ. Α., Joint Conference of Inorganic Chemistry of the Chemical Institute of Canada and the American Chemical Society on Catalytic Aspects of Metal Phosphine Complexes, Guelph, June, 1980. 9. Catellani, M.; Halpern, J., Inorg. Chem., 1980, 19, 566-568. 10. Yoshida, T.; Yamagata, T.; Tulip, T. H.; Ibers, J. Α.; Otsuka, S., J. Am. Chem. Soc., 1978, 100, 2063-2073. 11. Yoshida, T.; Okano, T.; Saito, K.; Otsuka, S., Inorg. Chim. Acta., 1980, 44, L135-L136. 12. Yoshida, T.; Okano, T.; Otsuka, S., J. Am. Chem. Soc., 1980, 102, 5966-5967. 13. Åkermark, B.; Johansen, H.; Roos, B.; Wahlgren, U., J . Am. Chem. Soc., 1979, 101, 5876-5883.
In Catalytic Activation of Carbon Monoxide; Ford, P.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
5. YOSHIDA ET AL. 14. 15.
Rh-Catalyzed Water Gas Shift
Tatsumi, Κ.; Hoffmann, R., J. Am. Chem. Soc., submitted for publication. Yoshida, T.; Thorn, D. L . ; Okano, T.; Ibers, J. Α.; Otsuka, S., J. Am. Chem. Soc., 1979, 101, 4212-4221. December 8, 1980.
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RECEIVED
In Catalytic Activation of Carbon Monoxide; Ford, P.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
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