Journal of the American Chemical Society
Communication
Fontaine, F. G. J. Am. Chem. Soc. 2013, 135, 9326. (g) Courtemanche,
M. A.; Legare, M. A.; Maron, L.; Fontaine, F. G. J. Am. Chem. Soc. 2014,
136, 10708. (h) Wang, T.; Stephan, D. W. Chem. Commun. 2014, 50,
7007. (i) Anker, M. D.; Arrowsmith, M.; Bellham, P.; Hill, M. S.; Kociok-
Kohn, G.; Liptrot, D. J.; Mahon, M. F.; Weetman, C. Chem. Sci. 2014, 5,
2826. (j) Fontaine, F. G.; Courtemanche, M. A.; Legare, M. A. Chem.
Eur. J. 2014, 20, 2990.
(10) For early reports of the Ru-catalyzed hydrogenation of CO2 to a
mixture of CO, CH3OH, and CH4, see: (a) Tominaga, K.; Sasaki, Y.;
Kawai, M.; Watanabe, T.; Saito, M. J. Chem. Soc., Chem. Commun. 1993,
629. (b) Tominaga, K.; Sasaki, Y.; Watanabe, T.; Saito, M. Bull. Chem.
Soc. Jpn. 1995, 68, 2837.
(11) Huff, C. A.; Sanford, M. S. J. Am. Chem. Soc. 2011, 133, 18122.
(12) For seminal work by Milstein demonstrating the 3- and 5-
catalyzed hydrogenation of esters, amides, and carbonates, see:
Balaraman, E.; Gunanathan, C.; Zhang, J.; Shimon, L. J. W.; Milstein,
D. Nat. Chem. 2011, 3, 609.
AUTHOR INFORMATION
■
Corresponding Author
Author Contributions
†N.M.R. and C.A.H. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by NSF under the CCI Center for
Enabling New Technologies through Catalysis (CENTC) Phase
II Renewal, CHE-1205189. C.A.H. thanks the NSF for a
Graduate Research Fellowship. N.M.R. and C.A.H. thank
Rackham Graduate School for a Rackham Merit Fellowship.
(13) (a) Wesselbaum, S.; vom Stein, T.; Klankermeyer, J.; Leitner, W.
Angew. Chem., Int. Ed. 2012, 51, 7499. (b) Wesselbaum, S.; Moha, V.;
Meuresch, M.; Brosinski, S.; Thenert, K. M.; Kothe, J.; Stein, T. v.;
REFERENCES
■
(1) (a) Kamijo, T.; Sorimachi, Y.; Shimada, D.; Miyamoto, O.; Endo,
T.; Nagayasu, H.; Mangiaracina, A. Energy Procedia 2013, 37, 813.
(b) Pera-Titus, M. Chem. Rev. 2013, 114, 1413.
(2) (a) Figueroa, J. D.; Fout, T.; Plasynski, S.; McIlvried, H.; Srivastava,
R. D. Int. J. Greenh. Gas Control 2008, 2, 9. (b) Yang, H.; Xu, Z.; Fan, M.;
Gupta, R.; Slimane, R. B.; Bland, A. E.; Wright, I. J. Environ. Sci. 2008, 20,
14. (c) Macdowell, N.; Florin, N.; Buchard, A.; Hallett, J.; Galindo, A.;
Jackson, G.; Adjiman, C. S.; Williams, C. K.; Shah, N.; Fennell, P. Energy
Environ. Sci. 2010, 3, 1645.
(3) (a) Corsten, M.; Ramírez, A.; Shen, L.; Koornneef, J.; Faaij, A. Int. J.
Greenh. Gas Control 2013, 13, 59. (b) Appel, A. M.; Bercaw, J. E.;
Bocarsly, A. B.; Dobbek, H.; DuBois, D. L.; Dupuis, M.; Ferry, J. G.;
Fujita, E.; Hille, R.; Kenis, P. J. A.; Kerfeld, C. A.; Morris, R. H.; Peden,
C. H. F.; Portis, A. R.; Ragsdale, S. W.; Rauchfuss, T. B.; Reek, J. N. H.;
Seefeldt, L. C.; Thauer, R. K.; Waldrop, G. L. Chem. Rev. 2013, 113,
6621.
Englert, U.; Holscher, M.; Klankermayer, J.; Leitner, W. Chem. Sci. 2015,
̈
6, 693.
(14) For a related approach that generates methyl formate from CO2,
see: Yadav, M.; Linehan, J. C.; Karkamkar, A. J.; van der Eide, E.;
Heldebrant, D. J. Inorg. Chem. 2014, 53, 9849.
(15) (a) Jacquet, O.; Frogneux, X.; Das Neves Gomes, C.; Cantat, T.
Chem. Sci. 2013, 4, 2127. (b) Beydoun, K.; Vom Stein, T.;
Klankermayer, J.; Leitner, W. Angew. Chem., Int. Ed. 2013, 52, 9554.
(c) Li, Y.; Sorribes, I.; Yan, T.; Junge, K.; Beller, M. Angew. Chem., Int. Ed.
2013, 52, 12156. (d) Beydoun, K.; Ghattas, G.; Thenert, K.;
Klankermayer, J.; Leitner, W. Angew. Chem., Int. Ed. 2014, 53, 11010.
(e) Sorribes, I.; Junge, K.; Beller, M. Chem.Eur. J. 2014, 20, 7878.
(16) John, J. M.; Bergens, S. H. Angew. Chem., Int. Ed. 2011, 50, 10377.
(17) Kuriyama, W.; Matsumoto, T.; Ogata, O.; Ino, Y.; Aoki, K.;
Tanaka, S.; Ishida, K.; Kobayashi, T.; Sayo, N.; Saito, T. Org. Process Res.
Dev. 2012, 16, 166.
(4) (a) Darensbourg, D. J. Inorg. Chem. 2010, 49, 10765. (b) Riduan, S.
N.; Zhang, Y. G. Dalton Trans. 2010, 39, 3347. (c) Dibenedetto, A.;
Angelini, A.; Stufano, P. J. Chem. Technol. Biotechnol. 2014, 89, 334.
(5) (a) Leitner, W. Angew. Chem., Int. Ed. 1995, 34, 2207. (b) Grabow,
L. C.; Mavrikakis, M. ACS Catal. 2011, 1, 365. (c) Choudhury, J.
ChemCatChem 2012, 4, 609. (d) Li, Y. H.; Junge, K.; Beller, M.
ChemCatChem 2013, 5, 1072. (e) Li, Y. N.; Ma, R.; He, L. N.; Diao, Z. F.
Catal. Sci. Technol. 2014, 4, 1498.
(6) (a) Waller, D.; Stirling, D.; Stone, F. S.; Spencer, M. S. Faraday
Discuss. Chem. Soc. 1989, 87, 107. (b) Spencer, M. S. Top. Catal. 1999, 8,
259.
(7) Martino, G.; Courty, P.; Marcilly, C.; Kochloefl, K.; Lunsford, J. H.
Handbook of Heterogeneous Catalysis; Wiley-VCH: Weinheim, 1997; p
1801.
(8) For examples of the use of boranes and silanes to convert CO2 to
the CH3OH oxidation state with homogeneous metal catalysts, see:
(a) Eisenschmid, T. C.; Eisenberg, R. Organometallics 1989, 8, 1822.
(b) Riduan, S. N.; Zhang, Y.; Ying, J. Y. Angew. Chem., Int. Ed. 2009, 48,
3322. (c) Chakraborty, S.; Zhang, J.; Krause, J. A.; Guan, H. J. Am. Chem.
Soc. 2010, 132, 8872. (d) Huang, F.; Lu, G.; Zhao, L.; Li, H.; Wang, Z. X.
J. Am. Chem. Soc. 2010, 132, 12388. (e) Huang, F.; Zhang, C.; Jiang, J.;
Wang, Z.-X.; Guan, H. Inorg. Chem. 2011, 50, 3816. (f) Riduan, S. N.;
Ying, J. Y.; Zhang, Y. G. ChemCatChem 2013, 5, 1490. (g) Wang, B. J.;
Cao, Z. X. R. Soc. Chem. Adv. 2013, 3, 14007. (h) LeBlanc, F. A.; Piers,
W. E.; Parvez, M. Angew. Chem., Int. Ed. 2014, 53, 789. (i) Anker, M. D.;
Arrowsmith, M.; Bellham, P.; Hill, M. S.; Kociok-Kohn, G.; Liptrot, D. J.;
Mahon, M. F.; Weetman, C. Chem. Sci. 2014, 5, 2826.
(18) (a) Balaraman, E.; Gnanaprakasam, B.; Shimon, L. J. W.; Milstein,
D. J. Am. Chem. Soc. 2010, 132, 16756. (b) Oldenhuis, N. J.; Dong, V.
M.; Guan, Z. Tetrahedron 2014, 70, 4213.
(19) TONs determined by GC-FID were in agreement with the values
established by NMR. For example, for Table 3, entry 1, the TONs for
methanol were 220
31 (NMR) and 180
23 (GC-FID). See
Supporting Information (SI) for details.
(20) (a) Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40.
(b) Hamilton, R. J.; Bergens, S. H. J. Am. Chem. Soc. 2006, 128, 13700.
(c) Clarke, M. L.; Diaz-Valenzuela, M. B.; Slawin, A. M. Z.
Organometallics 2007, 26, 16. (d) Saudan, L. A.; Saudan, C. M.;
Debieux, C.; Wyss, P. Angew. Chem., Int. Ed. 2007, 46, 7473. (e) Huff, C.
A.; Sanford, M. S. ACS Catal. 2013, 3, 2412. (f) Dub, P. A.; Henson, N.
J.; Martin, R. L.; Gordon, J. C. J. Am. Chem. Soc. 2014, 136, 3505.
(21) (a) Jessop, P. G.; Hsiao, Y.; Ikariya, T.; Noyori, R. J. Am. Chem.
Soc. 1994, 116, 8851. (b) Jessop, P. G.; Hsiao, Y.; Ikariya, T.; Noyori, R.
J. Am. Chem. Soc. 1996, 118, 344. (c) Jessop, P. G. The Handbook of
Homogeneous Hydrogenation; Wiley-VCH: Weinheim, 2008; p 489.
(22) The direct hydrogenation of DMFA to CH3OH is another
possible pathway. Although we cannot definitively rule this out, we
believe that it is unlikely based on (i) the observed conversion of DMFA
to DMF under the reaction conditions coupled with (ii) the higher
electrophilicity of DMF versus DMFA. Additionally, the hydrogenation
−
of HCO2 NEt3H+ (which cannot form the corresponding amide) under
conditions similar to those in eq 2 yielded <10 turnovers of CH3OH
(versus 99 turnovers for DMF hydrogenation). See SI for details.
(23) 95 °C was selected because this temperature was found to be
optimal for the hydrogenation of CO2 to DMF (see Table S3 for
details).
(9) For examples of the use of frustrated Lewis pairs for the conversion
of CO2 to CH3OH, see: (a) Ashley, A. E.; Thompson, A. L.; O’Hare, D.
Angew. Chem., Int. Ed. 2009, 48, 9839. (b) Menard, G.; Stephan, D. W. J.
́
Am. Chem. Soc. 2010, 132, 1796. (c) Stephan, D. W.; Erker, G. Angew.
Chem., Int. Ed. 2010, 49, 46. (d) Sgro, M. J.; Stephan, D. W. Angew.
Chem., Int. Ed. 2012, 51, 11343. (e) Zhu, J.; An, K. Chem.Asian J.
2013, 8, 3147. (f) Courtemanche, M. A.; Legare, M. A.; Maron, L.;
(24) The use of 13CO2 for this reaction resulted in the formation of
13CH3OH and H13C(O)NMe2 as the products, as determined by 1H and
13C NMR spectroscopic analysis. See SI for details.
D
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX