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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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