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COMMUNICATION
Journal Name
o
sample used as catalyst at 70 C in the IR cell. As evidenced in coupling of a wide range of silanes with alcohols. The change
DOI: 10.1039/C5CC10216B
Figure 3 the amount of Cu(I) probed by CO (characteristic IR in the oxidation state of Cu is visually observable by the
-1
band for Cu(I)-CO at 2123 cm ) increases once the sample has change of the colour. The relative reactivity of the substrates
been exposed to the reaction conditions.
seems to be primarily governed by their size and steric
encumbrance, this observation being compatible with the
occurrence of the reaction within the pores of the material. It
has been found that Cu (BTC) is reusable and its crystal
2
123
0
.2
3
2
structure is not affected by the reversible redox changes taking
place in Cu ions during the reaction and after exposure to
atmospheric oxygen. The present results constitute another
remarkable example illustrating the high potential of Cu MOFs
as catalysts for a variety of reactions such, as in this case, the
dehydrogenative coupling of silanes with alcohols.
c
b
a
2400
2200
2000
1800
-1
)
Wavenumber (cm
Notes and references
o
Figure 3. IR of adsorbed CO at 25 C on a) the fresh sample
ADM thanks University Grants Commission, New Delhi for the
award of Assistant Professorship under its Faculty Recharge
Programme. ADM also thanks Department of Science and
Technology, India, for the financial support through Fast Track
project (SB/FT/CS-166/2013) and the Generalidad Valenciana for
financial aid supporting his stay at Valencia through the
Prometeo programme. Financial support by the Spanish Ministry
of Economy and Competitiveness (CTQ-2012-32315 and Severo
Ochoa) and Generalidad Valenciana (Prometeo 2012-014) is
prior to the in situ IR cell reaction, and b) after in situ IR cell
o
reaction at 70 C in the presence of
1 with n-butanol, and c) in
the presence of phenylsilane and n-butanol.
On the other hand, n-butanol adsorption experiments shows
that this alcohol is only adsorbed on Cu(II) sites, since no
n-butanol adsorption was observed on Cu(I) species (Figure 4).
This IR study indicates that both Cu(II) and Cu(I) are gratefully acknowledged.
simultaneously required as active sites in the dehydrogenative
[
1] J. F. Blandez, A. Primo, A. M. Asiri, M. Alvaro and H. Garcia, Angew.
Si-O coupling reaction, thus, Cu(II) adsorbs the alcohol and
Cu(I) to interact with the silane.
Chem. Int. Ed. 2014, 53, 12581-12586.
[
2] P. G. Belelli, M. L. Ferreira and D. E. Damiani, J. Mol. Catal. A: Chem.
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Candu, S. Coman, V. Parvulescu and H. Garcia, Nature Commun. 2015
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M. Horáček, H. Garcia and J. Čejka, Catal. Sci. Technol. 2013, 3 500-507.
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011, 1, 856-867.
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,
b
a
1
[
4
[
2
[
1
[
,
1200
1120
1040
960
880
800
-1
Wavenumber (cm )
[
Figure 4. IR of n-butanol adsorption on activated sample a) and
o
on a H reduced sample at 150 C b). Black spectra correspond
2
[
2
to the sample before and red spectra after n-butanol
adsorption.
2
[
In summary, in the present work, it has been shown that
the oxidation state of Cu in Cu (BTC) can be quite reversibly
3
2
modified by silane or hydrogen evolved in the reaction
1
rendering a sufficiently high population of Cu(I) ions to act as [20] K. Fukumoto, M. Kasa and H. Nakazawa, Inorg. Chim. Acta 2015
efficient heterogeneous catalyst for the dehydrogenative 431, 219-221.
,
4
| J. Name., 2012, 00, 1-3
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