G Model
CATTOD-8964; No. of Pages15
ARTICLE IN PRESS
D. Vidick et al. / Catalysis Today xxx (2014) xxx–xxx
3
previous work [61], the number of acidic functions was estimated
at 1.7 mmol/g.
IR CO = 2077 (m), 2050 (s), 2033 (s), 2011 (s), 1989 (w), 1966
−
1
(w) 1818 (w) cm . Anal (calc.) = C 22.43 (22.78), H 1.10 (1)
. Cluster [Ru C(CO) (Au{PPh }) ] (7) was prepared by react-
%
6
16
3
2
2.1.2. Addition of SOCl2 on Cm-ox to give Cm-Cl
ing 100 mg of (PPN) [Ru C(CO) ] (0.0466 mmol) with 2 equiv.
2 6 16
In a 100 ml round-bottom flask, 500 mg of Cm-ox were intro-
duced and degassed overnight at 120 C. Then, 30 ml of toluene
of Au(PPh )Cl (46.1 mg, 0.0933 mmol) in 10 ml dichloromethane.
3
◦
The mixture was stirred at room temperature for 1 h, then fil-
tered and the solvent was removed under reduced pressure. The
obtained powder was purified by column chromatography on sil-
ica (hexane/dichloromethane 50/50) to give 5 as a dark red powder
were introduced together with 3 ml of SOCl . The mixture was
2
◦
refluxed (120 C) for 5 h, filtered, and the obtained powder was
extensively washed with toluene and dried under vacuum for sev-
eral hours to give Cm-Cl.
(77.7 mg, 84%). IR = 2067 (w), 2049 (s), 2017 (vs), 1965 (w), 1821
CO
−
1
(
m) cm [65]. Anal (calc.) = C 32.15 (32.07), H 1.64 (1.52) %. Cluster
2
.1.3. Addition of H N(CH ) NR on Cm-Cl to give Cm-NR2
In a 100 ml round-bottom flask, 450 mg of Cm-Cl were intro-
[Ru5C(CO)14(Au{PPh }) ] (8) was obtained in 75% yield by addition
2 2 2 2
3
2
of Au(PPh )Cl to (PPN) [Ru5C(CO) ] [66]. IR = 2065 (m), 2035
3 2 14 CO
−
1
duced together with 30 ml toluene. Then, 1.3 equiv. (with regard
to the number of acidic functions estimated in 450 mg of oxidized
Cm) of NH (CH ) NR (where R = H or CH ) were added (0.99 mmol,
(m), 2020 (s), 2008 (s), 1975 (m), 1845 (w) cm . Anal (calc.) = C
33.31 (33.51), H 1.64 (1.65) %. Cluster [Ru C(CO) (Au{PPh }) ]
4
12
3
2
(9) was obtained in 67% yield from cluster 8 in an autoclave [67].
IR CO = 2064 (vw), 2032 (s), 2022 (s), 2008 (w), 1990 (m), 1954
2
2
2
2
3
0
.07 ml for R = H; 0.99 mmol, 0.11 ml for R = CH ). The mixture was
3
◦
−1
refluxed (120 C) for 4 h to give Cm-NH2 or Cm-NMe . Finally, the
(w) cm . Anal (calc.) = C 34.94 (35.22), H 1.71 (1.81) %. Clus-
2
solid was filtered off, extensively washed with toluene and dried
under vacuum for several hours.
ter [Ru5PtC(CO)15(Au{PPh }) ] (10) was obtained in 73% yield by
3
2
reaction between Au(PPh )Cl and (PPh ) [Ru5PtC(CO) ] [68]. IR
3
4
2
15
CO = 2068 (m), 2038 (s), 2015 (vs), 1968 (m), 1859 (m), 1834 (m)
−
1
2.1.4. Addition of HPPh2 on Cm-NH2 to give Cm-PPh2
cm . Anal (calc.) = C 30.55 (30.45), H 1.70 (1.47) %.
In a 100 ml round-bottom flask, 2.5 equiv. (with regard to the
number of acidic functions estimated in 400 mg of oxidized Cm)
2.3. Grafting of clusters
of HPPh2 (1.7 mmol, 0.29 ml), and CH O (1.7 mmol, 51 mg) were
2
introduced with 7.5 ml of methanol. The mixture was stirred at
The amount of cluster engaged in each grafting experiment cor-
respond to a theoretical 5 wt.% metal loading on the support after
ligands removal. In the case of cluster 1, 12.2 mg of cluster 1 was
stirred with 95 mg of support in 20 ml toluene or THF at room tem-
perature for 5 days in the dark. The solid was filtered, washed with
solvent and dried at room temperature under vacuum. For cluster 2,
15 mg of this cluster was stirred with 95 mg of support in a 1:1 mix-
ture of acetone and THF (total volume = 20 ml) at room temperature
for 5 days in the dark. The solid was filtered washed with acetone
and dried at room temperature under vacuum. For clusters 3–10,
the procedure was the same for all clusters. For example, 8.7 mg
of cluster 3 was stirred with 95 mg of Cm-PPh2 in a 1:1 mixture of
toluene and dichloromethane (total volume = 20 ml) at room tem-
perature for 5 days in the dark. The solid was filtered, washed with
dichloromethane and dried at room temperature under vacuum.
The supported clusters were then submitted to a thermal treat-
ment in a tubular oven STF 16/450 from CARBOLITE. The samples
◦
7
0 C for 10 min and then cooled down to room temperature. At
the same time, 400 mg of Cm-NH2 were introduced with 12.5 ml
of methanol in a 100 ml round-bottom flask. Once the first mixture
reached room temperature, it was added to the Cm-NH suspension
2
and stirred for 15 min at room temperature. Then, 25 ml of toluene
◦
were added and the solution was stirred at 70 C for 24 h, to give
Cm-PPh . Finally, the solid was filtered out, extensively washed
2
with methanol and dried under vacuum for several hours.
2
.1.5. Addition of CF SO CH on Cm-NMe2 to give Cm-NMe +
3 3 3 3
In a 100 ml round-bottom flask, 400 mg of Cm-NMe were intro-
2
duced together with 200 ml of acetone. Then, 3 equiv. (with regard
to the number of acidic functions estimated in 400 mg of oxidized
Cm) of methyl trifluoromethanesulfonate were added (2.3 mmol,
0
.25 ml). The suspension was stirred at room temperature for 24 h,
filtered, extensively washed with acetone and finally dried under
vacuum for several hours to give Cm-NMe3+
.
were placed into porcelain combustion boats and heated under N
2
◦
◦
stream at 200 C for cluster 1, 300 C for 1 h for clusters 2–6 and at
◦
◦
2.2. Synthesis of clusters (see Annex 1 in Supplementary data for
350 C for 1 h for clusters 7–10 (heating ramp: 100 C/h).
infrared spectra)
2.4. Physico-chemical methods of characterization
Cluster [HFeCo (CO)12] (1) was obtained in 50% yield from
3
Fe(CO)5 and Co (CO) [58,62]. IR CO (CCl ) = 2100 (w), 2059
Infrared spectra of the clusters were recorded in
dichloromethane solution on a BRUKER EQUINOX 55 spectrometer
with a solution cell from PERKIN ELMER.
2
8
4
1
−
(
s), 2050 (s), 2027 (m), 1986 (m), 1883 cm
(s). Anal (calc.) = C
2
2.43 (25.30), H 0.23 (0.18) %. Cluster (NEt )[FeCo (CO)12] (2) was
4 3
obtained in 80% yield from Fe(CO)5 and Co (CO)8 [58,62]. IR
The elemental analyses (C, H, N) of clusters were realized by the
Analytical Chemistry service of University College London (UK).
The elemental analyses (C, H, N, O) of supports were realized by
MEDAC Ltd., UK.
2
CO
−
1
(
(
%
acetone) = 2063 (w), 2005 (s), 1970 (w), 1932 (m), 1823 cm
m). Anal (calc.) = C 34.17 (34.36), H 2.88 (2.88), N 1.99 (2.00)
. Cluster [Ru C(CO) ] (3) was obtained in 71% in an auto-
6
17
−
1
clave from [Ru (Co)12] [63]. IR CO = 2068 (s), 2047 (s) cm
.
XPS analyses were performed on a Kratos Axis Ultra spec-
trometer (Kratos Analytical, Manchester, UK) equipped with a
monochromatized aluminum X-ray source (powered at 10 mA and
15 kV). The sample powders were pressed into small stainless steel
troughs mounted on a multi specimen holder. The pressure in the
3
Cluster [Ru5C(CO)15] (4) was obtained in 89% yield from clus-
ter 3 in an autoclave [63]. IR (hexane) = 2068 (s), 2034 (m),
CO
−
018 (w) cm . (PPN) [Ru C(CO) ] and (PPN) [Ru5C(CO)14] were
2 6 16 2
1
2
obtained by reduction in KOH/MeOH [64] with a yield of 97 and
6%, respectively. Cluster [Ru PtC(CO)16(COD)] (5) was obtained
−
6
9
analysis chamber was about 10 Pa. The angle between the normal
to the sample surface and the direction of photoelectrons collection
6
in 31% yield by addition of Pt(COD)Cl2 to (PPN) [Ru C(CO)16]
2
6
◦
[
1
64]. IR CO = 2078 (m), 2035 (s), 2002 (m), 1975 (w), 1943 (w)
821 (w) cm . Anal (calc.) = C 20.59 (21.92), H 1.50 (0.88) %.
was about 0 . Analyses were performed in the hybrid lens mode, the
−1
In the latter conditions, the full width at half maximum (FWHM)
Cluster [Ru5PtC(CO)14(COD)] (6) was obtained in 67% yield by
the reaction between Pt(COD)Cl2 and (PPN) [Ru5C(CO)14] [64].
2
Please cite this article in press as: D. Vidick, et al., Phosphine- and ammonium-functionalized ordered mesoporous carbons as supports