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activation barrier. By applying steady-state approximation on Notes and references
+
[
k
[Fe]–H][R
3
Si–OH
2
] and making the reasonable assumption that
1
J. O. M. Bockris, Science, 1972, 176, 1323.
ꢀ
1
c k , the rate law immediately simplifies to (1), which is
2
2 L. Schlapbach and A. Zuttel, Nature, 2001, 414, 353–358.
3 R. F. Service, Science, 2004, 305, 958–961.
consistent with the results from our kinetic studies:
4
U. Eberle, M. Felderhoff and F. Sch u¨ th, Angew. Chem., Int. Ed., 2009,
8, 6608–6630.
5 US Department of Energy: Hydrogen Storage, http://www1.eere.
energy.gov/hydrogenandfuelcells/storage/current_technology.html,
accessed February 2014.
4
d½H2ꢄ
rate ¼
¼ kobs½organosilaneꢄ½waterꢄ½catalystꢄ
(1)
dt
k1k2
6
W. Sattler and G. Parkin, J. Am. Chem. Soc., 2012, 134, 17462–17465.
where kobs ¼
.
kꢀ1½MeCNꢄ
7 (a) R. Murugavel, A. Voigt, M. G. Walawalkar and H. W. Roesky,
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Further experiments were performed to study the effect of
acetonitrile on the rate of hydrolysis. Indeed, it was found that
when the concentration of acetonitrile was doubled successively,
the initial rate decreased by an average of 2.00 ꢃ 0.08 times. This
result confirms the inverse first-order dependence on acetonitrile,
2
010, 110, 1233–1277.
8 S. E. Denmark and C. S. Regens, Acc. Chem. Res., 2008, 41,
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R. Walsh, Acc. Chem. Res., 1981, 14, 246–252.
1
9
1
0 (a) N. Asao, Y. Ishikawa, N. Hatakeyama, Menggenbateer,
Y. Yamamoto, M. Chen, W. Zhang and A. Inoue, Angew. Chem.,
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which is in accordance with our derived kobs
.
In conclusion, we have shown that the hydrolytic oxidation of
organosilanes to produce dihydrogen and organosilanols can be
performed by using an iron-based catalyst which is air-stable and
exhibits excellent mediating power with turnover numbers
7533–7536; (c) W. Li, A. Wang, X. Yang, Y. Huang and T. Zhang,
Chem. Commun., 2012, 48, 9183–9185.
1
1
1 M. Yu, H. Jing and X. Fu, Inorg. Chem., 2013, 52, 10741–10743.
2 Y. Lee, D. Seomoon, S. Kim, H. Han, S. Chang and P. H. Lee, J. Org.
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4
2
ꢀ1
approaching 10 and turnover frequencies in excess of 10 min
for most of the organosilanes. A mechanism, consistent with our 13 E. A. Ison, R. A. Corbin and M. M. Abu-Omar, J. Am. Chem. Soc.,
2
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experimental data, has been proposed to further our current
understanding of the catalytic organosilane hydrolysis reaction.
The attractive characteristics of this iron complex may open
new opportunities in the development of hydrogen storage
materials derived from organosilanes for simple and cost-
effective on-demand hydrogen generation strategies.
1
1
2011, 30, 4008–4013.
1
1
5 P. J. Turrell, J. A. Wright, J. N. T. Peck, V. S. Oganesyan and
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7194 | Chem. Commun., 2014, 50, 7191--7194
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