Communications
Kühn, ChemSusChem 2016, 9, 2849; c) M. Iguchi, Y. Himeda, Y. Manaka,
H. Kawanami, ChemSusChem 2016, 9, 2749; d) C. Prichatz, M. Trincado,
L. Tan, F. Casas, A. Kammer, H. Junge, M. Beller, H. Grützmacher,
ChemSusChem 2018, 11, 3092; e) S. Wang, H. Huang, T. Roisnel, C.
Bruneau, C. Fischmeister, ChemSusChem 2019, 12, 179; f) C. Fink, G.
Laurenczy, Eur. J. Inorg. Chem. 2019, 2381; g) N. Onishi, R. Kanega, E.
Fujita, Y. Himeda, Adv. Synth. Catal. 2019, 361, 289.
work is significant on a fundamental level as it is one of only a
few to establish that a pathway involving MLC is not required
to generate highly active and productive dehydrogenation
catalysts.[17] It also suggests that further improvement in
catalysis can be achieved by lowering the barrier for decarbox-
ylation and improving catalyst stability. Future work in our
groups will focus on modifying the pincer ligand to solve these
challenges.
1
2
3
4
5
6
7
8
9
[8] a) F. Bertini, I. Mellone, A. Ienco, M. Peruzzini, L. Gonsalvi, ACS Catal.
2015, 5, 1254; b) M. Montandon-Clerc, A. F. Dalebrook, G. Laurenczy, J.
Catal. 2016, 343, 62; c) M. C. Neary, G. Parkin, Dalton Trans. 2016, 45,
14645.
[9] a) J. E. Heimann, W. H. Bernskoetter, N. Hazari, J. M. Mayer, Chem. Sci.
2018, 8, 6629; b) J. E. Heimann, W. H. Bernskoetter, N. Hazari, J. Am.
Chem. Soc. 2019, 141, 10520.
[10] N. Govindarajan, E. J. Meijer, Faraday Discuss. 2020, In Press.
[11] a) Y. Zhang, A. D. MacIntosh, J. L. Wong, E. A. Bielinski, P. G. Williard,
B. Q. Mercado, N. Hazari, W. H. Bernskoetter, Chem. Sci. 2015, 6, 4291;
b) J. B. Curley, N. E. Smith, W. H. Bernskoetter, N. Hazari, B. Q. Mercado,
Organometallics 2018, 37, 3846.
[12] For another example of cis/trans dihydride species implicated in (de)
hydrogenative catalysis, see: N. Gorgas, B. Stöger, L. F. Veiros, K.
Kirchner, ACS Catal. 2016, 6, 2664–2672.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Acknowledgements
NH and WHB acknowledge support from the U.S. Department of
Energy, Office of Science, Basic Energy Sciences, Catalysis Science
Program, under Award DE-SC0018222. JBC thanks the NSF for
support as a NSF Graduate Research Fellow. All computational
work was supported by the facilities and staff of the Yale
University Faculty of Arts and Sciences High Performance
Computing Center. We thank Maxim Secor, Sharon Hammes-
Schiffer, Lluis Artús Suarez, and Ainara Nova for guidance with
DFT calculations, Nicholas Smith for valuable discussions, and
Danielle Chirdon for assistance with GC quantification.
[13] Complex
3 is observed as a 5:1 mixture of 2 isomers at room
temperature. Only the major isomer is shown in the figures. Further
details about the isomers can be found in the SI, section SII.
[14] A same-excess experiment showed that a negligible amount of catalyst
decomposition occurs in the initial regime where we performed our
kinetic analysis (see SI). Therefore, we do not think that catalyst
decomposition influences our results.
[15] a) G. Bauer, K. A. Kirchner, Angew. Chem. Int. Ed. 2011, 50, 5798; b) B.
Zhao, Z. Han, K. Ding, Angew. Chem. Int. Ed. 2013, 52, 4744; c) O.
Eisenstein, R. H. Crabtree, New J. Chem. 2013, 37, 21; d) J. R. Khusnutdi-
nova, D. Milstein, Angew. Chem. Int. Ed. 2015, 54, 12236; e) D. G. Gusev,
ACS Catal. 2016, 6, 6967; f) I. Mellone, N. Gorgas, F. Bertini, M. Peruzzini,
K. Kirchner, L. Gonsalvi, Organometallics 2016, 35, 3344; g) L. Alig, M.
Fritz, S. Schneider, Chem. Rev. 2019, 119, 2681.
[16] U. Jayarathne, N. Hazari, W. H. Bernskoetter, ACS Catal. 2018, 8, 1338.
[17] a) A. N. Marziale, A. Friedrich, I. Klopsch, M. Drees, V. R. Celinski, J.
Schmedt auf der Günne, S. Schneider, J. Am. Chem. Soc. 2013, 135,
13342; b) J.-H. Choi, L. E. Heim, M. Ahrens, M. H. G. Prechtl, Dalton Trans.
2014, 43, 17248; c) X. Ye, P. N. Plessow, M. K. Brinks, M. Schelwies, T.
Schaub, F. Rominger, R. Paciello, M. Limbach, P. Hofmann, J. Am. Chem.
Soc. 2014, 136, 5923; d) D. Pingen, J.-H. Choi, H. Allen, G. Murray, P.
Ganji, P. W. N. M. van Leeuwen, M. H. G. Prechtl, D. Vogt, Catal. Sci.
Technol. 2018, 8, 3969; e) A. Agapova, E. Alberico, A. Kammer, H. Junge,
M. Beller, ChemCatChem 2019, 11, 1910.
Keywords: Homogeneous catalysis · Hydrogen storage · Iron
complexes · Pincer ligands · Mechanistic studies.
[1] a) N. S. Lewis, D. G. Nocera, Proc. Natl. Acad. Sci. USA 2006, 103, 15729;
b) O. Ellabban, H. Abu-Rub, F. Blaabjerg, Renewable Sustainable Energy
Rev. 2014, 39, 748; c) M. D. Burkart, N. Hazari, C. L. Tway, E. L. Zeitler, ACS
Catal. 2019, 9, 7937.
[2] U. Eberle, M. Felderhoff, F. Schuth, Angew. Chem. Int. Ed. 2009, 48, 6608.
[3] a) A. F. Dalebrook, W. Gan, M. Grasemann, S. Moret, G. Laurenczy, Chem.
Commun. 2013, 49, 8735; b) K. Sordakis, C. Tang, L. K. Vogt, H. Junge,
P. J. Dyson, M. Beller, G. Laurenczy, Chem. Rev. 2018, 118, 372.
[4] a) W.-H. Wang, Y. Himeda, J. T. Muckerman, G. F. Manbeck, E. Fujita,
Chem. Rev. 2015, 115, 12936; b) D. Mellmann, P. Sponholz, H. Junge, M.
Beller, Chem. Soc. Rev. 2016, 45, 3954; c) W. H. Bernskoetter, N. Hazari,
Acc. Chem. Res. 2017, 50, 1049.
[5] a) P. J. Chirik, T. B. Gunnoe, ACS Catal. 2015, 5, 5584; b) A. Fuerstner, ACS
Cent. Sci. 2016, 2, 778.
[6] E. A. Bielinski, P. O. Lagaditis, Y. Zhang, B. Q. Mercado, C. Würtele, W. H.
Bernskoetter, N. Hazari, S. Schneider, J. Am. Chem. Soc. 2014, 136, 10234.
[7] a) Z. Wang, S.-M. Lu, J. Li, J. Wang, C. Li, Chem. Eur. J. 2015, 21, 12592;
b) D. Jantke, L. Pardatscher, M. Drees, M. Cokoja, W. A. Herrmann, F. E.
Manuscript received: January 14, 2020
Revised manuscript received: January 15, 2020
Version of record online: ■■■, ■■■■
ChemCatChem 2020, 12, 1–6
5
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
��
These are not the final page numbers!