C. D. Nunes, M. Pillinger, A. A. Valente, J. Rocha, A. D. Lopes, I. S. Gonc˛alves
CDCl3, 25 °C, TMS): δ ϭ 0.60Ϫ0.68 (m, 4 H, SiCH2), 1.15Ϫ1.24 Ϫ108.9 (sh, Q4) ppm. Elemental analysis found C 10.94, N 1.25,
FULL PAPER
(m, 18 H, OCH2CH3), 1.76Ϫ1.86 (m,
4
H, CH2CH2CH2),
H 2.63, Mo 1.0.
3.40Ϫ3.44 (t, 4 H, NCH2), 3.73Ϫ3.84 (m, 12 H, OCH2CH3),
7.32Ϫ7.50 (m, 5 H, Ph), 7.57Ϫ7.75 (m, 3 H, Ph), 7.88Ϫ7.93 (m, 2
H, Ph) ppm. 13C{1H} NMR (75.47 MHz, CDCl3, 25 °C, TMS):
δ ϭ 8.0 (SiCH2), 18.3 (OCH2CH3), 24.3 (CH2CH2CH2), 56.4
(CH2NϭC), 58.1 (OCH2CH3), 127.2, 128.6, 129.1 (Ph), 166.3
(CH2NϭC) ppm. 29Si NMR (59.62 MHz, CDCl3, 25 °C, TMS):
δ ϭ Ϫ52.90 ppm. C32H52N2O6Si2 (616.99): calcd. C 62.30, H 8.50,
N 4.54; found C 62.00, H 8.41, N 4.28.
MCM-48-L/Me3SiCl (6): A solution of the ligand 1 (0.71 g,
1.15 mmol) in toluene (5 mL) was added to a suspension of MCM-
48 (1.15 g) in toluene (10 mL) and the mixture heated at 100 °C
for 9 h. After cooling to ambient temperature, Me3SiCl (5 mL) was
added and the mixture stirred at room temperature for a further
24 h. The so-obtained solid was then filtered off and washed twice
with acetone (2 ϫ 20 mL), twice with CH2Cl2 (2 ϫ 15 mL), and
dried in vacuo at 100 °C for 3 h. Selected FT Raman: ν˜ ϭ 3068
(s), 2971 (m), 2932 (s), 2901 (s), 1599 (s), 1550 (w), 1452 (m), 1414
MoO2Cl2[Ph-DAB-(CH2)3Si(OEt)3]
(2):
A
solution
of
(w), 1028 (w), 1001 (s), 617 (m) cmϪ1 13C CP MAS NMR: δ ϭ
.
MoO2Cl2(THF)2 (0.25 g, 0.75 mmol) in THF (10 mL) was treated
with 1 equivalent of the ligand 1 in THF (5 mL). The resulting
turbid solution was stirred for a further 30 min at room tempera-
ture. The solvent was then evaporated, and the resultant solid prod-
uct washed with hexane and dried in vacuo. Yield: 0.47 g, 76%. IR
(KBr): ν˜ ϭ 2973 (s), 1681 (s), 1674 (vs), 1594 (s), 1491 (m), 1449
(s), 1306 (m), 1230 (m), 1077 (vs), 1047 (vs), 984 (s), 943 (vs), 915
Ϫ0.3 (Me3SiOϪ), 9.3 (SiCH2), 17.0, 20.8, 58.9, 128.2 (phenyl-C)
ppm. 29Si MAS NMR: δ ϭ Ϫ109.6 ppm. 29Si CP MAS NMR: δ ϭ
13.9 (Me3SiOϪ), Ϫ50.0 (T1), Ϫ58.4 (T2), Ϫ67.5 (T3), Ϫ101.9 (Q3),
Ϫ109.4 (Q4) ppm. Elemental analysis found C 13.38, N 1.30, H
2.33.
(vs), 879 (s), 774 (m), 703 (m), 684 (m), 643 (m) cmϪ1
MAS NMR: 9.6 (SiCH2), 18.3 (OCH2CH3), 21.7
(CH2CH2CH2), 55.0 (CH2NϭC), 58.4 (OCH2CH3), 128.8 (Ph),
167.5 (CH2NϭC) ppm. 29Si MAS NMR: δ
Ϫ54.4 ppm.
.
13C CP
MCM-48-L/Me3SiCl/MoO2Cl2 (7): A solution of MoO2Cl2(THF)2
(0.52 g, 1.5 mmol) in CH2Cl2 (5 mL) was added to a suspension of
the ligand-silica 6 (1.0 g) in CH2Cl2 (10 mL) and the mixture stirred
overnight at room temperature. The resultant solid was then filtered
off and washed with CH2Cl2 (4 ϫ 20 mL), and dried in vacuo at
room temperature for 3 h. Selected FT Raman: ν˜ ϭ 3066 (m), 2962
δ
ϭ
ϭ
C32H52Cl2MoN2O8Si2 (816.90): calcd. C 46.99, H 6.65, N 3.42;
found C 46.56, H 6.29, N 3.38.
(m), 2903 (s), 1598 (m), 1001 (m) cmϪ1 13C CP MAS NMR: δ ϭ
.
MCM-41/MoO2Cl2[Ph-DAB-(CH2)3Si(OEt)3] (3): A solution of 2
(0.40 g, 0.49 mmol) in CH2Cl2 (10 mL) was added to a suspension
of MCM-41 (1.0 g) in CH2Cl2 (15 mL) and the mixture stirred at
room temperature for 24 h. The solution was then filtered and the
so-obtained pale blue powder washed repeatedly with CH2Cl2 (4 ϫ
20 mL), before drying in vacuo at room temperature for several
hours. IR (KBr): ν˜ ϭ 1633 (m), 1596 (w), 1450 (m), 1384 (w), 1230
0.7 (Me3SiOϪ), 8.7 (SiCH2), 17.5, 20.7, 58.9, 128.7 (phenyl-C),
184.4 ppm. 29Si MAS NMR: δ ϭ 14.8, Ϫ55.0 (bd), Ϫ108.7 ppm.
29Si CP MAS NMR: δ ϭ 14.7 (Me3SiOϪ), Ϫ54.7 (T1), Ϫ59.4 (T2),
Ϫ67.5 (T3), Ϫ108.7 (Q4) ppm. Elemental analysis found C 10.94,
N 1.30, H 2.63, Mo 1.4.
Catalysis: The liquid-phase epoxidation of cyclooctene was carried
out at 55 °C under air in a micro reaction vessel equipped with a
magnetic stirrer, which was loaded with complex (0.073 mmol) or
MCM-catalyst (175 mg), olefin (7.3 mmol) and TBHP (11 mmol,
5.5 in decane). Samples were withdrawn periodically and ana-
lysed using a gas chromatograph (Varian 3800) equipped with a
capillary column (SPB-5, 20 m ϫ 0.25 mm ϫ 0.25 µm) and a flame
ionisation detector. Undecane was used as internal standard added
after the reaction.
(sh), 1078 (vs), 954 (m), 914 (sh), 798 (m), 568 (m), 455 (s) cmϪ1
.
13C CP MAS NMR: δ ϭ 8.7, 15.6, 21.1, 53.2, 58.8, 128.7, 131.7,
136.6, 137.9 ppm. 29Si MAS NMR: δ ϭ Ϫ50.4, Ϫ56.2, Ϫ102.6
(Q3), Ϫ108.0 (Q4) ppm. Elemental analysis found C 8.50, N 0.49,
H 0.90, Mo 3.3.
MCM-41-L/Me3SiCl (4): A solution of the ligand 1 (0.66 g,
1.07 mmol) in toluene (5 mL) was added to a suspension of MCM-
41 (1.0 g) in toluene (10 mL) and the mixture heated at 100 °C for
9 h. After cooling to ambient temperature, Me3SiCl (5 mL) was
added and the mixture stirred at room temperature for a further
24 h. The resultant solid was then filtered off and washed twice
with acetone (2 ϫ 20 mL), twice with CH2Cl2 (2 ϫ 15 mL), and
dried in vacuo at 100 °C for 3 h. Selected FT Raman: ν˜ ϭ 3069
(m), 2961 (m), 2904 (s), 1600 (s), 1552 (w), 1452 (m), 1415 (w),
Acknowledgments
The authors are grateful to FCT, POCTI, and FEDER for finan-
cial support (Project PCTI/1999/QUI/32889). CN thanks the Uni-
versity of Aveiro and the FCT for research grants. Paula Branda˜o
´
and Claudia Morais are acknowledged for assistance with the
1028 (w), 1001 (s), 617 (m) cmϪ1 13C CP MAS NMR: δ ϭ Ϫ0.5
.
NMR experiments.
(Me3SiOϪ), 8.4 (SiCH2), 16.4, 20.8, 24.9, 57.8, 127.6 (phenyl-C)
ppm. 29Si MAS NMR: δ ϭ 14.5 (bd), Ϫ53.8 (bd), Ϫ109.5 ppm.
29Si CP MAS NMR: δ ϭ 13.8 (Me3SiOϪ), Ϫ54.0 (T1), Ϫ58.5 (T2),
Ϫ67.5 (T3), Ϫ102.0 (sh, Q3), Ϫ108.8 (sh, Q4) ppm. Elemental
analysis found C 16.24, N 1.34, H 2.33.
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MCM-41-L/Me3SiCl/MoO2Cl2 (5): A solution of MoO2Cl2(THF)2
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the ligand-silica 4 (1.0 g) in CH2Cl2 (10 mL) and the mixture stirred
overnight at room temperature. The resultant solid was then filtered
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room temperature for 3 h. Selected FT Raman: ν˜ ϭ 3069 (m), 2962
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Ϫ0.3 (Me3SiOϪ), 9.3 (SiCH2), 20.8, 25.0, 57.9, 128.5 (phenyl-C).
29Si MAS NMR: δ ϭ 14.6, Ϫ55.0 (bd), Ϫ110.0 ppm. 29Si CP MAS
NMR: δ ϭ 14.4 (Me3SiOϪ), Ϫ54.0 (T1), Ϫ58.0 (T2), Ϫ67.5 (T3),
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