M.S. Saraiva et al. / Journal of Organometallic Chemistry 751 (2014) 443e452
451
[MoI2(CO)3(MeCN)2] (0.5 mmol, 0.2575 g) also in methanol. The
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ52.4 (T1), ꢀ60.6 (T2), ꢀ70.4
mixture was stirred overnight, under inert atmosphere. The brown
solid formed was filtered, washed with diethyl ether and dried
under vacuum.
(T3), ꢀ96.6 (Q2), ꢀ103.1 (Q3), ꢀ114.6 (Q4).
4.2.6. Silica-Pr-1 and silica-Pr-2
Yield: 0.252 g, yield 83%. Anal. Calc. for MoI2N2O4C16H10: C
29.84, H 1.57, N 4.35. Found: C 29.48, H 2.03, N 4.67.
The complex 1 or 2 (3 mmol) was dissolved in dimethylforma-
mide, and then triethylamine (3.8 mmol) was added. 1 g of silica-
Pr-Cl was added to this solution, at 273 K, and then left at room
temperature for 12 h. The suspension was filtered, washed with
2 ꢂ 20 mL dichloromethane, and dried under vacuum.
IR (KBr, n
/cmꢀ1): 3411 (vs), 3231 (w), 3088 (w), 3038 (w), 2952
(w), 2908 (w), 2846 (w), 2735 (w), 2066 (s), 2001 (s), 1957 (s), 1923
(s), 1856 (m), 1622 (s), 1558 (m), 1462 (m), 1458 (m), 1239 (m), 1102
(m), 1082 (m), 744 (m).
1H NMR (400.10 MHz, DMSO, r.t.,
d
ppm): 7.17 (t, 1H, H5 ), 7.25 (d,
4.2.6.1. Silica-Pr-1. Anal. Found: C 2.79, H 0.64, N 0.41, Mo 0.52.
0
1H, H3 ), 7.60 (m, 3H, H4 /H5/H6), 7.87 (m, 2H, H4/H7), 8.07 (H6 ).
IR (KBr,
(w), 1867 (w), 1652 (m), 1105 (vs), 802 (m), 473 (s).
13C CP/MAS (DD) NMR (
ppm): 9.0 (SieCH2), 25.8 (eCH2e), 64.6
n
/cmꢀ1): 3425 (s), 2952 (w), 2917 (w), 2871 (w), 1998
0
0
0
13C NMR (100.25 MHz, DMSO, r.t.,
d
ppm): 109.7 (C1 ), 114.5 (C4/
0
0
0
0
0
C7), 117.7 (C3 ), 120.6 (C5 ), 126.3 (C5/C6), 129.6 (C6 ), 135.5 (C4 ), 147.0
d
0
(C8/C9), 157.6 (C2/C2 ).
(CleCH2), 115-160 broad band aromatic carbons.
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ60.6 (T2), ꢀ65.5 (T3), ꢀ93.3
4.2.3. MCM-Pr-Cl
(Q2), ꢀ104.8 (Q3), ꢀ112.96 (Q4).
2.0 mL of 3-(chloropropyl)trimethoxysilane was added to a
suspension of 1 g of MCM-41 in 30 mL of toluene, and allowed to
reflux for 24 h. The yellow suspension was filtered, washed with
4 ꢂ 20 mL dichloromethane, and dried under vacuum.
Anal. Found: C 7.21, H 1.73.
4.2.6.2. Silica-Pr-2. Anal. Found: C 5.11, H 1.04, N 1.62, Mo 0.029.
IR (KBr,
/cmꢀ1): 3400 (vs), 2924 (w), 2910 (w), 2839 (w), 2744
n
(w), 2007 (w), 1838 (w), 1653 (vs), 1456 (w), 1402 (w), 1308 (m),
1224 (s), 1090 (vs), 779 (m), 613 (w), 453 (m).
IR (KBr,
n
/cmꢀ1): 3404 (vs), 2934 (w), 2911 (w), 2844 (w), 1621
13C CP/MAS (DD) NMR (
d ppm): 9.8 (SieCH2), 25.4 (eCH2e), 65.9
(m), 1615 (m), 1384 (m), 1218 (s), 1066 (vs), 937 (w), 789 (m), 668
(w), 568 (w), 448 (s).
(CleCH2).
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ60.6 (T2), ꢀ72.0 (T3), ꢀ94.95
13C CP/MAS (DD) NMR (
d
ppm): 9.8 (SieCH2), 26.1 (eCH2e),
(Q2), ꢀ106.4 (Q3), ꢀ116.2 (Q4).
45.8, 46.9 (CleCH2).
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ48.5 (T1), ꢀ57.4 (T2), ꢀ66.7
4.3. Catalytic tests
(T3), ꢀ92.5 (Q2), ꢀ100.6 (Q3), ꢀ110.9 (Q4).
The complexes and materials were tested in the catalytic
epoxidation of cis-cyclooctene (cy8), 1-octene (1-oct), styrene (sty),
geraniol (ger), cis-hex-3-en-1-ol (cis), trans-hex-2-en-1-ol (trans)
and R(þ)-limonene (R-lim), using tert-butylhydroperoxide (TBHP)
as oxidant. The catalytic oxidation tests were carried out at 328 K
under normal atmosphere in a reaction vessel equipped with a
magnetic stirrer and a condenser. In a typical experiment the vessel
was loaded with olefin or alcohol (100 mol%), internal standard
(dibutyl ether), catalysts (1 mol%), oxidant (200 mol%), and 3 mL of
solvent. Addition of the oxidant determines the initial time of the
reaction. The course of the reactions was monitored by quantitative
GC-analysis by collecting samples at 10, 30 min, 1 h and 1.5 h, then
at 2, 4, 6, 8, and 24 h of reaction. These samples were treated as
described previously prior to injection in the GC column [43].
4.2.4. MCM-Pr-1 and MCM-Pr-2
The complex 1 or 2 (3 mmol) was dissolved in dimethylforma-
mide, and then triethylamine (3.8 mmol) was added. 1 g of MCM-
Pr-Cl was added to this solution, at 273 K, and then left at room
temperature for 12 h. The suspension was filtered, washed with
2 ꢂ 20 mL dichloromethane, and dried under vacuum.
4.2.4.1. MCM-Pr-1. Anal. Found: C 14.42, H 3.12, N 3.09, Mo 0.59.
IR (KBr, n
/cmꢀ1): 3390 (vs), 3224 (w), 2939 (w), 2922 (w), 2870
(w), 2792 (w), 2008 (w),1923 (w),1842 (w),1655 (s), 1483 (w),1385
(w), 1234 (m), 1053 (vs), 943 (s), 781 (m), 442 (s).
13C CP/MAS (DD) NMR (
d
ppm): 10.5 (SieCH2), 26.6 (eCH2e),
47.6 (CleCH2).
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ58.0 (T2), ꢀ66.2 (T3), ꢀ91.8
(Q2), ꢀ101.2 (Q3), ꢀ110.2 (Q4).
4.3.1. Epoxidation of cis-cyclooctene (cy8), 1-octene (1-oct), styrene
(sty), R(þ)-limonene(R(þ)-lim), geraniol (ger), cis-3-hexen-1-ol
(cis), and trans-2-hexen-1-ol (trans)
Substrate (800 mg: 7.3 mmol of cis-cyclooctene, 7.7 mmol of
styrene, 5.2 mmol of geraniol, 7.1 mmol of 1-octene, 5.87 mmol of
R(þ)-limonene, 7.99 mmol of cis-hex-3-en-1-ol, and 7.99 mmol of
trans-hex-2-en-1-ol, 800 mg dibutyl ether (internal standard),
1 mol% of catalyst, 2.65 mL of TBHP (5.5 M in n-decane) and 3 mL of
dichloromethane (CH2Cl2)).
4.2.4.2. MCM-Pr-2. Anal. Found: C 16.42, H 3.52, N 3.85, Mo 1.16.
IR (KBr,
/cmꢀ1): 3390 (vs), 3219 (w), 2931 (w), 2920 (w), 2868
n
(w), 2792 (w), 2008 (w), 1842 (w), 1655 (vs), 1483 (w), 1437 (w),
1385 (m), 1232 (m), 1053 (vs), 945 (m), 781 (m), 447 (s).
13C CP/MAS (DD) NMR (
d
ppm): 10.4 (SieCH2), 26.5 (eCH2e),
47.5 (CleCH2).
29Si CP/MAS (DD) NMR (
d
ppm): ꢀ58.0 (T2), ꢀ66.5 (T3), ꢀ91.0
(Q2), ꢀ101.1 (Q3), ꢀ109.9 (Q4).
Acknowledgements
4.2.5. Silica-Pr-Cl
2.0 mL of 3-(chloropropyl)trimethoxysilane was added to a
suspension of 1 g of silica in 30 mL of toluene, and allowed to reflux
for 24 h. The yellow suspension was filtered, washed with
4 ꢂ 20 mL dichloromethane, and dried under vacuum.
Anal. Found: C 1.56, H 0.51.
The authors thank FCT, POCI and FEDER (projects PTDC/QUI/
71576/2006, PEst-OE/QUI/UI0612/2013, PEst-OE/QUI/UI0100/2013)
for financial support. MSS and CIF thank FCT for research grants
(SFRH/BD/48640/2008 and SFRH/BD/81029/2011).
IR (KBr,
(vs), 946 (m), 789 (m), 462 (s).
13C CP/MAS (DD) NMR (
ppm): 9.6 (SieCH2), 26.1 (eCH2e), 45.8
(CleCH2).
n
/cmꢀ1): 3373 (s), 2886 (w), 1622 (w), 1205 (vs), 1080
References
d