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ACS Catalysis
one of the most active first row transition metal catalysts discovered
(6) Roseblade, S. J.; Pfaltz, A. Acc. Chem. Res. 2007, 40, 1402-
1411.
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to date. The nickel-catalyzed method was scaled and successfully
executed with standard laboratory glassware without the need for
high-pressure equipment. Deuterium labeling experiments with
trisubstituted cyclic alkenes demonstrate that reversible "-
hydrogen elimination and alkyl migration is operative during the
hydrogenation cycle, resulting in observation of a host of deuterat-
ed isotopologues. Investigations into the nature of the active species
with both the in situ generated catalyst and the isolated, dimeric
precursor demonstrated the role of the borane in the activation of
dihydrogen, accounting for the observed enhancement in activity
(7) (a) Chirik, P. J. Acc. Chem. Res. 2015, 48, 1687-1695. (b)
Darcel, C.; Sortais, J.-B. In Iron Catalysis II; Bauer, E., Ed.;
Springer International Publishing: Cham, 2015; pp 173–216.
(c)
(8) For a few recent examples of Co- and Fe-catalyzed hydrogena-
tion: (a) Friedfeld, M. R.; Shevlin, M.; Hoyt, J. M.; Krska, S.
W.; Tudge, M. T.; Chirik, P. J. Science 2013, 342, 1076-1080.
(b) Friedfeld, M. R.; Margulieux, G. W.; Schaefer, B. A.; Chi-
rik, P. J. J. Am. Chem. Soc. 2014, 136, 13178-13181. (c) Tok-
mic, K; Markus, C. R.; Zhu, L.; Fout, A. R. J. Am. Chem. Soc.
2016, 138, 11907-11913. (d) Gieshoff, T. N.; Chakraborty, U.;
Villa, M.; Jacobi von Wangelin, A. Angew. Chemie Int. Ed.
2017, 56, 3585-3589.
(9) Yu, R. P.; Darmon, J. M.; Hoyt, J. M.; Margulieux, G. W.;
Turner, Z. R.; Chirik, P. J. ACS Catal. 2012, 2, 1760-1764.
(10) Yu, R. P.; Darmon, J. M.; Milsmann, C.; Margulieux, G.
W.; Stieber, S. C. E.; DeBeer, S.; Chirik, P. J. J. Am.
Chem. Soc. 2013, 135, 13168-13184.
(11) Pappas, I.; Treacy, S.; Chirik, P. J. ACS Catal. 2016, 6,
4105-4109.
(12) Palmer, W. N.; Zarate, C.; Chirik, P. J. J. Am. Chem. Soc.
2017, 139, 2589-2592.
(13) A low-valent !-diimine iron complex has demonstrated activi-
ty for the hydrogenation of 1-hexene: Bart, S. C.; Hawrelak, E.
J.; Lobkovsky, E.; Chirik, P. J. Organometallics 2005, 24, 5518-
5527.
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upon addition of HBPin. The modularity of the !-diimine suggests
that new catalyst libraries, including asymmetric variants, should be
possible and investigations into these catalyst types is currently
under study.
ASSOCIATED CONTENT
Supporting Information
Complete experimental details including pre-catalyst optimization
studies, and characterization data for deuterated products. This materi-
AUTHOR INFORMATION
Corresponding Author
* pchirik@princeton.edu
(14) Sanfilippo, D.; Rylander, P. N. Hydrogenation and Dehydro-
genation. Ullmann's Encyclopedia of Industrial Chemistry.
Wiley-VCH Verlag GmbH & Co. KGaA, 2009.
(15) Zaramello, L.; Albuquerque, B. L.; Domingos, J. B.; Philippot,
K. Dalton Trans. 2017, 46, 5082-5090.
ACKNOWLEDGMENT
We thank the National Science Foundation GOALI (CHE-1564379)
for financial support. N.G.L. thanks the National Science Foundation
(NSF) for a Graduate Research Fellowship (DGE-1148900). We
thank Dr. W. Neil Palmer for assistance in the preparation of
[(iPrDI)NiH]2. We also thank Michael Shevlin (Merck) and Dr. Istvan
Pelczer for helpful discussions and experimental assistance.
(16) Connelly Robinson, S. J.; Heinekey, D. M. Chem. Commun.,
2017, 53, 669-676.
(17) (a) Angulo, I. M.; Kluwer, A. M.; Bouwman, E. Chem. Com-
mun. 1998, 2689-2690. (b) Angulo, I. M.; Bouwman, E. J.
Mol. Catal. A: Chemical 2001, 175, 65-72. (c) Angulo, I. M.;
Bouwman, E.; Lutz, M.; Mul, W. P.; Spek, A. L. Inorg. Chem.
2001, 40, 2073-2082. (d) Angulo, I. M.; Lok, S. M.; Quiroga
Norambuena, V. F.; Lutz, M.; Spek, A. L.; Bouwman, E. J. Mol.
Catal. A: Chemical 2002, 187, 55-67. (e) Angulo, I. M.;
Bouwman, E.; van Gorkum, R.; Lok, S. M.; Lutz, M.; Spek, A.
L. J. Mol. Catal. A: Chemical 2003, 202, 97-106. (f) Mooi-
broek, T. J.; Wenker, E. C. M.; Smit, W.; Mutikainene, I.; Lutz,
M.; Bouwman, E. Inorg. Chem. 2013, 52, 8190-8201.
(18) (a) Wu, J.; Faller, J. W.; Hazari, N.; Schmeier, T. J. Organome-
tallics 2012, 31, 806-809. (b) Vasudevan, K. V.; Scott, B. L.;
Hanson, S. K. Eur. J. Inorg. Chem. 2012, 4898-4906. (c) Har-
man, W. H.; Peters, J. C. J. Am. Chem. Soc. 2012, 134, 5080-
5082. (d) Lin, T.-P.; Peters, J. C. J. Am. Chem. Soc. 2014, 136,
13672-13683. (e) Cammarota, R. C.; Lu, C. C. J. Am. Chem.
Soc. 2015, 137, 12486-12489.
REFERENCES
(1) Hartwig, J. Organotransition Metal Chemistry: From
Bonding to Catalysis; University Science Books: Sausali-
to, CA, 2010; p 575-665.
(2) (a) Crabtree, R. H. The Organometallic Chemistry of the
Transition Metals, 2nd ed; Wiley: New York, 1994. (b)
Chaloner, P. A.; Esteruelas, M. A.; Joó, F.; Oro, L. A. Homoge-
neous Hydrogenation; Kluwer Academic Publishers: Dor-
drecht, The Netherlands, 1994. (c) Schrock, R. R.; Osborn, J.
A. J. Am. Chem. Soc. 1971, 93, 2397-2407. (d) Knowles, W. S.
Angew. Chem. Int. Ed. 2002, 41, 1998-2007. (e) Noyori, R.
Angew. Chem. Int. Ed. 2002, 41, 2008-2022.
(3) (a) Crabtree, R. H.; Felkin, H.; Morris, G. E. J. Organomet.
Chem., 1977, 141, 205-215. (b) Crabtree, R. H. Acc. Chem.
Res., 1979, 12, 331–337.
(4) (a) Cui, X.; Burgess, K. Chem. Rev., 2005, 105, 3272-3296;
(b) Church, T. L.; Andersson, P. G. Coord. Chem. Rev., 2008
,
(19) Wang, Y.; Kostenko, A.; Yao, S.; Driess, M. J. Am. Chem. Soc.
2017, 139, 13499-13506.
(20) (a) Yang, P.; Xu, H.; Zhou, J. Angew. Chem. Int. Ed.
2014, 53, 12210-12213. (b) Guo, S.; Yang, P.; Zhou, J.
Chem. Commun. 2015, 51, 12115-12117.
252, 513-531. (c) Kraft, S.; Ryan, K.; Kargbo, R. B. J. Am.
Chem. Soc., 2017, 139, 11630-11641.
(5) (a) Broene, R. D.; Buchwald, S. L. J. Am. Chem. Soc. 1993
,
115, 12569-12570. (b) Troutman, M. V.; Appella, D. H.;
Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 4916-4917. (c)
Grossman, R. B.; Doyle, R. A.; Buchwald, S. L. Organometal-
lics 1991, 10, 1501-1505.
(21) Shevlin, M.; Friedfeld, M. R.; Sheng, H.; Pierson, N. A.; Hoyt,
J. M.; Campeau, L.-C.; Chirik, P. J. J. Am. Chem. Soc. 2016
138, 3562-3569.
,
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