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Carbene-Based Lewis Pairs for Hydrogen Activation
Jason W.
Runyon
A
D
,
Oliver
Steinhof
A
,
H. V. Rasika
Dias
B
C
,
Joseph C.
Calabrese
B
,
William J.
Marshall
B
and
Anthony J.
Arduengo
A
D
A
Department of Chemistry, The University of Alabama, 3068 Shelby Hall, Tuscaloosa, AL 35487-0336, USA.
B
Central Research and Development Department, E. I. du Pont de Nemours & Company, Experimental Station E500/1808, Wilmington, DE 19880-0500, USA.
C
Current address: Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019-0065, USA.
D
Corresponding authors. Email: jwrunyon@crimson.ua.edu,aj@ajarduengo.net
Australian Journal of Chemistry
64(8)
1165-1172 http://dx.doi.org/10.1071/CH11246
Submitted: 17 June 2011 Accepted: 22 June 2011 Published:
19
August
2011
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Abstract
A series of Lewis acid–base pairs containing sterically demanding carbenes were investigated for hydrogen activation that could potentially be reversible for use in hydrogen storage applications. When electron-rich boranes are employed as electrophiles, the imidazolium cation is reduced to a 2H-imidazoline (aminal). The aminals were synthesized independently by reduction of imidazolium cations with strong reducing agents. Carbocations were also found to act as electrophiles for hydrogen activation. Preliminary results revealed that it is possible to reduce an alcohol to an alkane using hydrogen gas as a reducing agent in these systems. Finally, it was demonstrated that a transition metal can be used as an electrophile to activate hydrogen through heterolytic cleavage. 
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References
[1]
(a) G. C. Welch, R. R. San Juan, J. D. Masuda, D. W. Stephan, Science 2006, 314, 1124. | CrossRef | CAS |  (b) G. C. Welch, D. W. Stephan, J. Am. Chem. Soc. 2007, 129, 1880. | CrossRef | (c) P. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan, Angew. Chem. 2007, 119, 8196. | CrossRef |
[2]
(a) A. J. Arduengo III, D. A. Dixon, Main Group Element Chemistry for Hydrogen Storage and Avtivation US Department of Energy Center of Excellence for Chemical Hydrogen Storage Report, 24 May 2005 Available online at: http://www.docstoc.com/docs/922349/Main-Group-Element-Chemistry-for-Hydrogen-Storage-and-Activation (accessed 07/07/11) (b) G. D. Frey, V. Lavallo, B. Donnadieu, W. W. Schöller, G. Bertrand, Science 2007, 316, 439. | CrossRef | (c) D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389. | CrossRef |
[3]
(a) D. Holschumacher, T. Bannenberg, C. G. Hrib, P. G. Jones, M. Tamm, Angew. Chem. Int. Ed. 2008, 47, 7428. | CrossRef | CAS | (b) E. Theuergarten, D. Schlüns, J. Grunenberg, C. G. Daniliuc, P. G. Jones, M. Tamm, Chem. Commun. 2010, 46, 8561. | CrossRef | (c) S. Kronig, E. Theuegarten, D. Holschumacher, T. Bannenberg, C. G. Daniliuc, P. G. Jones, M. Tamm, Inorg. Chem. 2011, 50, | CrossRef |
[4]
(a) A.-L. Schmitt, G. Schnee, R. Welter, S. Dagorne, Chem. Commun. 2010, 46, 2480. | CrossRef | CAS | (b) E. Aldeco-Perez, A. J. Rosenthal, B. Donnadieu, P. Parameswaran, G. Frenking, G. Bertrand, Science 2009, 326, 556. | CrossRef | (c) L. N. Appelhans, D. Zuccaccia, A. Kovacevic, A. Chianese, J. R. Miecznikowski, A. Macchioni, E. Clot, O. Eisenstein, R. H. Crabtree, J. Am. Chem. Soc. 2005, 127, 16299. | CrossRef |
[5]
D. Holschumacher, C. Taouss, T. Bannenberg, C. G. Hrib, C. G. Daniliuc, P. G. Jones, M. Tamm, Dalton Trans. 2009, , 6927. | CrossRef | CAS |
[6]
O. Steinhof, Investigations in the Field of Carbene-Boron Chemistry. MSc Diploma Thesis, Technische Universität Carolo-Wilhelmina zu Braunschweig and The University of Alabama-Tuscaloosa, 2003.
[7]
A. J. Arduengo, S. F. Gamper, M. Tamm, J. C. Calabrese, F. Davidson, H. Craig, J. Am. Chem. Soc. 1995, 117, 572. | CrossRef | CAS |
[8]
(a) B. M. Mikhailov, T. K. Baryshnikova, V. G. Kiselev, A. S. Shashkov, Bull. Acad. Sci. USSR, Div. Chem. Sci. 1979, 2361, 2367. (b) B. M. Mikhailov, V. N. Smirnov, V. A. Kasparov, Bull. Acad. Sci. USSR, Div. Chem. Sci. 1976, 2148, 21.
[9]
E. A. Mistryukov, Mendeleev Commun. 2006, 16, 258. | CrossRef |
[10]
(a) P. C. Ford, Acc. Chem. Res. 1981, 14, 31. | CrossRef | CAS | (b) B. D. Dombek, J. Am. Chem. Soc. 1980, 102, 6855. | CrossRef |
[11]
(a) F. Feigl, P. Krumholtz, Monatsh. Chem. 1932, 59, 314. | CrossRef | CAS | (b) M. Smith, R. Bau, J. Am. Chem. Soc. 1973, 95, 2388. | CrossRef | (c) H. W. Walker, P. G. Pearson, P. C. Ford, J. Am. Chem. Soc. 1983, 105, 1179. | CrossRef |
[12]
M. B. Smith, R. Bau, J. Am. Chem. Soc. 1973, 95, 2388. | CrossRef | CAS |
[13]
K. Öfele, C. Kreiter, Chem. Ber. 1972, 105, 529. | CrossRef |
[14]
G. Huttner, W. Gartzke, Chem. Ber. 1972, 105, 2714. | CrossRef | CAS |
[15]
D. D. Perrin, W. L. F. Armarengo, Purification of Laboratory Chemicals 1988 (Pergamon Press: Oxford).
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