©Research Institute for Integrated Science, Kanagawa University
عේ ⪺ع 2004-2005ᐕᐲᄹᎹᄢቇห⎇ⓥᅑബഥᚑ⺰ᢥ
ⅣႺ⺞ဳ㍲ߩ․㐳ࠍ↢߆ߒߚᣂⷙ㉄ൻ⸅ᇦߩഃᚑߣ
ࠛࡀ࡞ࠡⅣႺ㗴߳ߩዷ㐿
ട⮮⍮㚅
1,3㊁ችஜม
1 ੫
1㋈ᧁቄ⋥
2Polyoxometalates and Microporous Transition Metal Carboxylates:
Synthesis, Characterization, and Oxidation Catalysis
Chika Nozaki Kato
1,3, Kenji Nomiya
1, Wasuke Mori
1and Suechika Suzuki
21 Department of Chemistry, and
2 Department of Biological Sciences, Faculty of Science, Kanagawa University, Hiratsuka-City, Kanagawa 259-1293, Japan
3 To whom correspondence should be addressed. E-mail: katouc06@kanagawa-u.ac.jp
Abstract: The oxidation of alkenes and alcohols with hydrogen peroxide (H2O2) and molecular oxygen, is quite an interesting objective for both academic and industrial fields. In this paper, we focused on polyoxometalates and microporous transition metal carboxylates as oxidation catalysts. For H2O2-based epoxidation reactions catalyzed by dimeric mono-, di-, and tri-titanium (IV)-substituted Keggin polyoxotungstates, tri-titanium (IV) - substituted Keggin polyoxotungstate was the most active because it exhibited the fastest formation rate of active hydroperoxotitanium (IV) intermediate. Furthermore, we investigated a novel method for the grafting reaction of transition metal-substituted polyoxometalates onto a silica surface.
Keggin-type vanadium(V)-substituted polyoxomolybdate (PMoV) was electrostatically anchored to a modified silica surface having cationic ammonium moiety. The PMoV-grafted silica material exhibited activities higher than those of homogeneous PMoV reactions for the oxidation of various alcohols with 1 atm dioxygen in the presence of isobutyraldehyde (IBA). Microporous copper(II) carboxylates showed unique activities for the oxidation of alcohols with H2O2 in a heterogeneous system, in which a green-colored species, H2[Cu2II,II (OOCC6H10COO)2(O2)]·H2O was one of the active oxidizing intermediates.
Keywords: polyoxotungstate, microporous copper(II) carboxylate, alkene epoxidation,
a
lcohol oxidation, grafting methodᐨ⺰
㘻ਇ㘻ൻ᳓⚛߿ࠕ࡞ࠦ࡞ߩ㉄ൻᔕߪޔ Ꮏᬺ⊛ᯏวᚑ⊛ߦᭂߡ㊀ⷐߢࠆ 1)ޕߎࠇ߹
ߢ᭽ޘߥ㉄ൻ⸅ᇦᔕ♽߇㐿⊒ߐࠇߡ߈ߡࠆ߇ޔ
ⅣႺߦኂߥ㉄ൻߩ↪߿ᄙ㊂ߦ↢ᚑߔࠆ↢ᚑ
‛ߩᑄ᫈ޔߐࠄߦߪ⸅ᇦߦ߹ࠇࠆ㊀㊄ዻߩಣℂ╬
߇㗴ߣߥߞߡࠆᔕࠪࠬ࠹ࡓ߽ዋߥߊߥޕ
৻ᣇޔㆊ㉄ൻ᳓⚛߿ಽሶ⁁㉄⚛ࠍ㉄ൻߣߒߚ
ൻ᳓⚛ޔࠕ࡞ࠦ࡞ޔ⧐㚅ᣖൻว‛╬ߩ㉄ൻᔕߪޔ ߘߩ↢ᚑ‛߇㉄⚛ߣ᳓ߩߺߢࠆߚޔⅣႺో
ߩὐ߆ࠄᵈ⋡ࠍ㓸ߡࠆޕ․ߦޔಽሶ⁁㉄⚛ࠍ㉄
ൻߣߒߚ㉄ൻᔕߪޔⅣႺోߩὐߛߌߢߥߊޔ
ࠦࠬ࠻߿ขࠅᛒߩ◲ଢߐߩὐ߆ࠄ߽↪ߢࠆޕ
ߒ߆ߒߥ߇ࠄޔಽሶ⁁㉄⚛ߪ㉄ൻߣߒߡߩᵴᕈ߇ ૐߚޔ㜞᷷ᐲ㜞ജࠍᔅⷐߣߒޔᎿᬺൻߔࠆ ߦߪ㗴ὐ߇ᄙޕ
ߘߎߢᧄ⎇ⓥߢߪޔࡐ㉄Ⴎߣ࠽ࡁ⚦ሹࠍ߽ߟࠞ
࡞ࡏࡦ㉄㊄ዻ㍲ߩ2♽⛔ߩൻว‛ࠍ㉄ൻ⸅ᇦߣߒ ߡ↪ޔએਅߩ3ߟߩ࠹ࡑߦ㑐ߒߡ⎇ⓥࠍⴕߞߚޕ Ԙಽሶ⁁㉄⚛ࠍ㉄ൻߣߒߚ㉄ൻᔕߦ㜞ᵴᕈࠍ␜
ߔ⸅ᇦߩಽሶ⸳⸘ࠍ⋡ᜰߒߡޔ߹ߕޔࠤࠡࡦဳ࠴࠲
ࡦ(IV)৻ޔੑޔਃ⟎឵ࡐ㉄Ⴎࠍ⸅ᇦߦ↪ߡㆊ㉄
ൻ᳓⚛ࠍ㉄ൻߣߒߚࠕ࡞ࠤࡦߩࠛࡐࠠࠪൻᔕࠍ ⴕޔᵴᕈὐ᭴ㅧߣ⸅ᇦᵴᕈߣߩ⋧㑐ߦߟߡᬌ⸛
ߒߚޕԙ⛯ߡޔဋ৻♽㉄ൻ⸅ᇦߣߒߡ㜞ᵴᕈࠍ␜
ߔࡐ㉄Ⴎߩਇဋ৻♽㉄ൻ⸅ᇦ߳ߩᔕ↪ࠍ⋡ᜰߒߡޔ ᵴᕈὐ᭴ㅧߩ៊ᄬήߊࡐ㉄Ⴎࠍࠪࠞ㕙߳࿕
ቯൻߔࠆᣇᴺࠍᬌ⸛ߒߚޕᧄ⎇ⓥߢߪޔࡃ࠽ࠫ࠙ࡓ (V)৻⟎឵ࡦࡕࡉ࠺ࡦ㉄Ⴎࠍߦߣߞߡޔࠗ࠰ࡉ
࠴࡞ࠕ࡞࠺ࡅ࠼ሽਅߢߩࠕ࡞ࠦ࡞ߩ㉄⚛㉄ൻߦ ߟߡᬌ⸛ߒߡࠆޕԚ৻ᣇޔ࠽ࡁ⚦ሹࠍ߽ߟࠪࠢ
ࡠࡋࠠࠨࡦࠫࠞ࡞ࡏࡦ㉄㌃(II)㍲ࠍ࿕⸅ᇦߣߒ ߡ↪ޔਇဋ৻♽ߢߩㆊ㉄ൻ᳓⚛ߦࠃࠆࠕ࡞ࠦ࡞
ߩ㉄ൻࠍⴕޔᔕਛ㑆ߢࠆ㌃(II)-ࡍ࡞ࠝࠠ࠰
⒳ߩන㔌᭴ㅧ⸃ᨆࠍⴕߞߚޕ
ዏޔ࿁ߩഥᚑ⎇ⓥ࠹ࡑԘ㨪Ԛߦ㑐ߔࠆᚑᨐߪ
ోߡኾ㐷ߦ⊒ߒߚ 2㨪4)ޕߎߩႎ๔ᦠߢߪⷐὐࠍ ㅀߴࠆߦߣߤࠆ߇ޔ⚦ߦߟߡߪߘߜࠄࠍෳᾖ ߐࠇߚޕ
᧚ᢱߣᣇᴺ
(Bu4N)7H[(a-PTiW11O39)2O](1)ߩวᚑ2)
[(PTiW11O39)2O]8-࠹ ࠻ ࡉ ࠴ ࡞ ࠕ ࡦ ࡕ ࠾ ࠙ ࡓ Ⴎ (TBA Ⴎ)ߩวᚑߪޔᣢߦႎ๔ߐࠇߡࠆࡈࠕ
ࠪ࠶࠼ဳߩวᚑᴺࠍᡷ⦟ߒߡⴕߞߚ 5)ޕએਅߦޔߘ ߩᣇᴺࠍ⸥ߔޕ࠼ࡈ࠻ਛߢޔTiCl4 (0.43 mL)ࠍ110 mLߩK7[a-PW11O39]·8H2O (4.6 g, 1.47 mmol)᳓ṁ ᶧߦട߃ࠆޕߎߩή⦡ㅘṁᶧࠍ 30 ಽ㑆ㆶᵹߒޔ ࡔࡦࡉࡦࡈࠖ࡞࠲(J. G. type, 0.2 mm)ߢࠈㆊߒ ߚޕߘߩࠈᶧߦㆊߩBu4NBr (10.6 g, 0.83 mmol) ࠍട߃ࠆߣ⊕⦡ᴉᲚ߇↢ᚑߔࠆޕߎߩ⊕⦡ಽᢔᶧࠍ 1ᤨ㑆ᡬᜈᓟޔ⊕⦡ᴉᲚࠍࡔࡦࡉࡦࡈࠖ࡞࠲(J.
G. type, 0.2mm)ߢ࿁ߒߚޕߎߩ☻ᴉᲚࠍ0͠ߢࠕ
࠻࠾࠻࡞/᳓߆ࠄౣᴉᲚߔࠆߎߣߦࠃࠅ♖ߒޔ
᳓(50 mL´3)ޔࠛ࠲ࡁ࡞(50mL ´ 3)ޔࠛ࠹࡞(50 mL´3)ߢᵞᵺߒߡ⋡⊛‛ࠍᓧߚޕ㊂(₸):4.26g (80.2%)ޕర⚛ಽᨆ: ታ᷹୯ (⸘▚୯): C, 19.08%
(18.78%); H, 3.63% (3.56%); N, 1.52% (1.37%)ޕࠞ
࠙ࡓߪᬌߐࠇߥ߆ߞߚ(0.021%)ޕIR (cm-1):
1070vs [n(P-O)], 964vs, 887vs, 808vs, 652s [n(Ti-O-Ti)], 594w, 517mޕ31P NMR (CD3CNਛ):d -13.12ޕTG/DTA: 20.3%ߩ㊀㊂ᷫޕ⊒ᾲࡇࠢࠍ 319.3, 337.0, 376.6, 435.7 °Cߦ᷹ⷰߒߚޕߎߩ㊀㊂
ᷫߪޔ7 ߩ TBA+ߩಽ⸃(23.7%)ߦኻᔕߒߡߚޕ ๆ⌕ߒߚ᳓ߦࠃࠆ㊀㊂ᷫߥߒޕ
(Bu4N)7KH2[(a-1,2-PTi2W10O38)2O2](2)ߩวᚑ2) [(a-1,2-PTi2W10O38)2O2]10-ߩ TBA ႮߩวᚑߪޔpH 2.2ߩ㉄ᕈਅޔ[(a-1,2-PTi2W10O38)2O2]10-ߩࠞ࠙ࡓ Ⴎ᳓ṁᶧ(0.8 g, 0.144 mmol)6)ߦㆊߩBu4NBr(9.5 g, 29.4 mmol)ߦട߃ࠆߎߣߢⴕߞߚޕ30ಽ㑆ᡬᜈ ᓟޔ⊕⦡ᴉᲚࠍࡔࡦࡉࡦࡈࠖ࡞࠲(J. G. type, 0.2 mm)ߢ࿁ߒޔ᳓(50 mL´2)ޔࠛ࠲ࡁ࡞(50
mL´2)ޔࠛ࠹࡞(50 mL´2)ߢᵞᵺߒߚޕߎߩ☻ᴉ Ლࠍ 0°C ߢࠕ࠻࠾࠻࡞/㈶㉄ࠛ࠴࡞߆ࠄߩౣᴉ Ლߦࠃࠅ♖ߒޔࠛ࠲ࡁ࡞(50 mL)ޔࠛ࠹࡞(50 mL)ߢᵞᵺߒߚޕ㊂(₸):0.27 g (28.3%)ޕర⚛ಽ ᨆ:ታ᷹୯ (⸘▚୯):C, 19.75% (19.45%); H, 3.73%
(3.70%); N, 1.76% (1.42%); K, 0.58% (0.57%)ޕIR (cm-1): 1097vs [n(P-O)], 962vs, 887vs, 809s, 686s [n(Ti-O-Ti)], 595w, 519mޕ31P NMR (CD3CNਛ):d -11.37ޕTG/DTA:22.1%ߩ㊀㊂ᷫޕ⊒ᾲࡇࠢࠍ 311.1, 321.9, 394.2 °Cߦ᷹ⷰߒߚޕߎߩ㊀㊂ᷫߪޔ 7ߩTBA+ߩಽ⸃(24.5%)ߦኻᔕߒߡߚޕๆ⌕ߒ ߚ᳓ߦࠃࠆ㊀㊂ᷫߥߒޕ
(Bu4N)7KH4[(a-1,2,3-PTi3W9O37)2O3](3)ߩวᚑ2) [(a-1,2,3-PTi3W9O37)2O3]12-ߩTBAႮߩวᚑߪޔpH 2.2 ߩ㉄ᕈਅޔ[(a-1,2,3-PTi3W9O37)2O3]12-ߩࠞ࠙
ࡓႮ᳓ṁᶧ(1.0 g, 0.18 mmol)7)ߦㆊߩ Bu4NBr (2.3 g, 7.0 mmol)ࠍട߃ࠆߎߣߢⴕߞߚޕ30ಽ㑆ᡬ ᜈᓟޔ⊕⦡ᴉᲚࠍࡔࡦࡉࡦࡈࠖ࡞࠲(J. G. type, 0.2mm)ߢ࿁ߒޔ᳓(50 mL ´ 2)ޔࠛ࠲ࡁ࡞(50 mL
´ 2)ޔࠛ࠹࡞(50 mL ´ 2)ߢᵞᵺߒߚޕ㊂(₸):
0.39g(32.8%)ޕర⚛ಽᨆ:ታ᷹୯ (⸘▚୯): C, 20.42%
(20.29%); H, 3.58% (3.89%); N, 1.58% (1.48%); K, 0.66% (0.59%)ޕIR (cm-1): 1063s [n(P-O)], 963vs [W-Ot], 889s [W-Oc], 822s [W-Oe], 738, 699s [n(Ti- O-Ti)], 594 w, 520 mޕ31P NMR (CD3CNਛ):d -10.15ޕ TG/DTA: 23.4%ߩ㊀㊂ᷫޕ⊒ᾲࡇࠢߪޔ309.6, 331.0 °Cߦ᷹ⷰߒߚޕߎߩ㊀㊂ᷫߪޔ7ߩTBA+ ߩ ಽ⸃(25.6%)ߦኻᔕߒߡߚޕๆ⌕ߒߚ᳓ߦࠃࠆ㊀㊂
ᷫߥߒޕ
K4[PMo11VVO40] (PMoV)ߩࠪࠞ㕙߳ߩ࿕ቯൻ3) ࠕࡕ࡞ࡈࠔࠬࠪࠞ (Azmax, 200m2/g) ࠍ 25 ºC ߢ2ᤨ㑆ੇ῎ߒߚޕߎߩߣ߈ߩࠪࠞ㕙ߩOH ၮߩᢙߪޔ4.67 OH groups/nm2ޔ1.55 mmol OH groups/g8)ޕߎߩੇ῎ߐߖߚࠪࠞ(1.0 g)ࠍ80 mL ߩࡔ࠲ࡁ࡞ߦಽᢔߒޔ0.28, 2.78, 8.34 mL (0.5, 5.0, and 15.0 mmol)ߩ(MeO)3Si(CH2)3N(CH3)3Cl ࠍട߃ߚޕߎߩᷙว‛ࠍ 80ºCߢ6ᤨ㑆ㆶᵹߒߚޕ ᓧࠄࠇߚ⊕⦡ᴉᲚࠍ࿁ߒޔࡔ࠲ࡁ࡞(10 mL ´ 3) ߢᵞᵺߒߚޕర⚛ಽᨆ [0.5 mmolߩࠪࡦࠞ࠶ࡊ
ࡦࠣ ࠍ ↪ ߒ ߚ႐ว] ታ ᷹ ୯: C, 1.93%; H, 0.16%;N,0.42%. ⸘ ▚ ୯ :(SiO2)59(Si(CH2)3- N(CH3)3Cl)(0.27 mmolºSi(CH2)3N(CH3)3Cl groups/g):
C, 1.94%;H, 0.41%; N, 0.38%ޕBET 㕙Ⓧ: 138 m2/gޕర⚛ಽᨆ [5.0 mmolߩࠪࡦࠞ࠶ࡊࡦࠣ
ࠍ↪ߚ႐ว] ታ᷹୯: C, 2.81%; H, 0.20%; N, 0.75%ޕ⸘▚୯: (SiO2)40(Si(CH2)3- N(CH3)3Cl) (0.39
mmol ºSi(CH2)3N(CH3)3Cl group/g): C, 2.81%; H, 0.59%; N, 0.55%ޕ BET㕙Ⓧ: 130 m2/gޕర⚛ಽ ᨆ [15.0 mmolߩࠪࡦࠞ࠶ࡊࡦࠣࠍ↪ߚ႐ ว] ታ᷹୯: C, 2.90%; H, 0.35%; N, 0.50%ޕ⸘▚୯: (SiO2)43(Si(CH2)3N- (CH3)3Cl) (0.36 mmol ºSi(CH2)
3N(CH3)3Cl groups/g): C, 2.62%; H, 0.55%; N, 0.51%ޕ ర⚛ಽᨆ⚿ᨐ߆ࠄޔࠪࡦࠞ࠶ࡊࡦࠣߩᦨᄢᜂ ᜬ㊂ߪޔ0.39 mmol ºSi(CH2)3N(CH3)3Cl groups/g ߢߞߚޕ
ߎߩࠪࡦࠞ࠶ࡊࡦࠣᜂᜬࠪࠞ (1.0 g, 0.27, 0.39 mmol ºSi(CH2)3N(CH3)3Cl groups/g)ࠍ
᳓(40 mL)ߦ30ಽ㑆ᡬᜈߒߚޕߎߎ߳ޔ᳓(50 mL) ߦ ṁ ⸃ ߒ ߚ K4[PMo11VVO40]·7H2O (1.03 g, 0.5 mmol)ࠍട߃ޔ25 ºCߢ24ᤨ㑆ᡬᜈߒߚޕᓧࠄࠇ࿕
ࠍ࿁ߒޔ᳓(30 mL´3)ߢᵞᵺᓟޔ2 ᤨ㑆ಓ⚿ੇ
῎ߒߚޕర⚛ಽᨆ [0.27 mmolߩࠪࡦࠞ࠶ࡊࡦ
ࠣࠍᜂᜬߒߚࠪࠞࠍ↪ߒߚ႐ว] ታ᷹୯: N, 0.66%; P, 0.16%; Si, 38.3%; Cl, < 0.02%; K, <
0.01%ޕ ⸘ ▚ ୯: {(SiO2)59}(Si(CH2)3N(CH3)3)4- (PMo11VO40)(H2O)15 (0.057 mmol PMoV/g): N, 0.32%; P, 0.18%; Si, 38.4%ޕర⚛ಽᨆ [0.39 mmol ߩࠪࡦࠞ࠶ࡊࡦࠣࠍᜂᜬߒߚࠪࠞࠍ↪ߒ ߚ႐ว] ታ᷹୯: N, 0.50%; P, 0.17%; Si, 37.9%; Cl, 0.21%; K, < 0.01%. ⸘▚୯: {(SiO2)40}(Si(CH2)3N- (CH3)3)4(PMo11VO40)(H2O)5 (0.082 mmol PMoV/g):
N, 0.46%; P, 0.25%; Si, 37.54%ޕ
[CuII,II2(OOCC6H10COO)2]·H2O(4)ߩวᚑ
⸥ߩൻว‛ߩวᚑ߅ࠃ߮ࠠࡖࠢ࠲࡚ࠪࡦ ߪޔᢥ₂9)ߦᓥߞߡⴕߞߚޕ
H2[Cu2II,II(OOCC6H10COO)2(O2)]×H2O(5)ߩวᚑ4) [CuII,II2(OOCC6H10COO)2]·H2O(100 mg, 206 mmol) ߩࠕ࠻࠾࠻࡞ಽᢔṁᶧߦޔ30% H2O2 ᳓ṁᶧ (648.8 mL, 8.24 mmol)ࠍട߃ߚޕቶ᷷ߢ4ᤨ㑆ᡬᜈ ᓟޔᓧࠄࠇߚ✛⦡☳ࠍ࿁ߒޔࠕ࠻࠾࠻࡞(50 mL ´ 3)ޔࡔ࠲ࡁ࡞(50 mL ´ 3)ߢᵞᵺߒߚޕߘߩ ᓟ 2 ᤨ㑆ಓ⚿ ੇ῎ߒ ߚ ޕ㊂(₸): 94.5 mg (87.8 %)ޕర⚛ಽᨆ: ታ᷹୯: C, 37.00; H, 4.66%ޕ
⸘▚ ୯: C16H24O11Cu2 = H2[Cu2(C8H10O4)2(O2)]
H2O: C, 37.07; H, 4.47 %ޕTG/DTA: 5.35 %ߩ㊀㊂
ᷫޕ⊒ᾲࡇࠢߪ 132.8 °C ߦ᷹ⷰߒߚޕߎࠇߪ Cu(H2O2)⒳ߩಽ⸃(6.5 %)ߦኻᔕߒߚޕᯏ㈩ሶߩ ಽ⸃ߪޔ242.7 °Cߩ⊒ᾲࡇࠢࠍߞߡ245 °Cઃ ㄭ߆ࠄ (54.26 %ߩ㊀㊂ᷫ)᷹ⷰߐࠇߚޕIR (cm-1):
1594s, 1511w, 1423s, 1373w, 1332w, 1297m, 1222w, 1045w, 929w, 784m, 767m, 727w, 526mޕ BET㕙Ⓧ: 328.4 m2/gޕ⚦ሹᓘ: 4.9 Åޕ⓸⚛ᦨᄢ
ๆ⌕㊂: 1.09 mol/mol of copperޕDR UV-vis: lmax
260, 385, 665 nmޕࡑࡦࠬࡍࠢ࠻࡞: 805 [n(O-O)]
cm-1ޕ
㉄ൻ⸅ᇦᔕ2 – 4)
࠴࠲ࡦ⟎឵ࡐ㉄Ⴎޔࡃ࠽ࠫ࠙ࡓ⟎឵ࡐ㉄Ⴎ࿕ቯ ൻࠪࠞޔ࠽ࡁ⚦ሹࠍ߽ߟࠪࠢࡠࡋࠠࠨࡦࠫࠞ࡞ࡏ ࡦ㉄㌃(II)㍲ࠍ⸅ᇦߣߒߚㆊ㉄ൻ᳓⚛߅ࠃ߮ಽሶ
⁁㉄⚛ߦࠃࠆࠕ࡞ࠤࡦޔࠕ࡞ࠦ࡞ߩ㉄ൻ⸅ᇦᔕ
᧦ઙߦߟߡߪޔTable 1 – 3ࠍෳᾖߐࠇߚޕ↢ᚑ
‛ߩಽᨆߪޔߕࠇߩᔕߩ႐ว߽ࠟࠬࠢࡠࡑ࠻ࠣ
ࡈࠖ(TCD, DB-FFAP ࠠࡖࡇࠞࡓ(0.53 mm´ 15 m); FID, DB-WAXࠠࡖࡇࠞࡓ(0.53 mm ´ 15 m))ߣ 㜞ㅦᶧ ࠢ ࡠ ࡑ ࠻ࠣ ࡈ ࠖ (Shim-pack VP-ODS 150 mm L ´ 4.6 mm ID)ߢ ⴕߞߚޕ
⚿ᨐߣ⸛⺰
ࠤࠡࡦဳ࠴࠲ࡦ(IV)1㨪3 ⟎឵ࡐ㉄Ⴎࠍ⸅ᇦߦ↪
ߚH2O2ߦࠃࠆࠕ࡞ࠤࡦߩࠛࡐࠠࠪൻᔕԘ2) [(a-PTiW11O39)2O]8- (1)ޔ[(a-PTi2W10O38)2O2]10- (2)ޔ [(a-PTi3W9O37)2O3]12- (3) (࿑1)ࠍ⸅ᇦߣߒߚㆊ㉄ൻ
᳓⚛ߦࠃࠆࠪࠢࡠࠝࠢ࠹ࡦޔࠪࠢࡠࡋࠠࡦޔ1-ࠝ
ࠢ࠹ࡦߩ㉄ൻᔕ⚿ᨐࠍ1ߦ␜ߔޕߕࠇߩၮ⾰
ࠍ↪ߚ႐ว߽ޔൻว‛ 3߇ൻว‛1ޔ2 ࠃࠅ߽⪺
ߒߊ㜞࠲ࡦࠝࡃ㗫ᐲ(TOF)ࠍ␜ߔߎߣ߇ಽ ߆ߞߚޕߎࠇߪޔ࠴࠲ࡦ৻ේሶᒰߚࠅߢ TOF ࠍ⸘
▚ߒߚ႐วߢ߽ห᭽ߢߞߚޕ
ߐࠄߦޔ⸅ᇦᵴᕈߦኻߔࠆࡊࡠ࠻ࡦᢙߩᓇ㗀ߦߟ
ߡᬌ⸛ߔࠆߣ(࿑2)ޔߕࠇߩൻว‛ࠍ⸅ᇦߦ↪ߚ ႐ว߽ࡊࡠ࠻ࡦᢙߩჇടߦߞߡᵴᕈߪ⋥✢⊛ߦჇ ടߒߚޕ
ߒ߆ߒߥ߇ࠄޔࡐ㉄Ⴎ৻ಽሶᒰߚࠅߩࡊࡠ࠻ࡦ ᢙࠍ⛔৻ߒߡ⸅ᇦᵴᕈࠍᲧセߒߡ߽ޔൻว‛3߇ൻ ว‛1,2ߦᲧߴߡ⪺ߒߊ㜞ᵴᕈߢߞߚޕᓥߞߡޔ
↪ߚ⸅ᇦߩᵴᕈὐ᭴ㅧ߇ᵴᕈߦ⪺ߒᓇ㗀ࠍਈ߃
(a) (b) (c)
࿑1. 1(a),2(b),3(c)ߩᄙ㕙᭴ㅧࡕ࠺࡞. 㤥⦡ߩ
㕙ߪ࠴࠲ࡦේሶࠍἯ⦡ߩ྾㕙ߪ PO4ࠍ
␜ߔ.
ߡ߅ࠅޔൻว‛3ߩA-Ti3ࠨࠗ࠻߇ᧄ㉄ൻᔕߦᦨ
߽㜞ᵴᕈࠍ␜ߔᵴᕈὐ᭴ㅧߢࠆߎߣ߇ಽ߆ߞߚޕ ߘߎߢޔᔕਛ㑆ߢࠆࡂࠗ࠼ࡠࡍ࡞ࠝࠠ࠰⒳
ߩ↢ᚑࠍ᷹ⷰߔࠆߚޔㆊ㉄ൻ᳓⚛ሽਅߢߩ
UV-vis᷹ቯࠍⴕߞߚޕߘߩ⚿ᨐޔ400 nmઃㄭߦ㉄
⚛⒳ߦࠃࠆᣂߒๆᏪࠍ᷹ⷰߒߚޕߎߩᲑ㓏ߢߪޔ ਇᵴᕈߥࡍ࡞ࠝࠠ࠰⒳߇↢ᚑߒߡࠆߩ߆ᵴᕈߥࡂ
ࠗ࠼ࡠࡍ࡞ࠝࠠ࠰⒳߇↢ᚑߒߡࠆߩ߆ࠍߢ߈ ߥޕߘߎߢޔㆊ㉄ൻ᳓⚛ሽਅߢࠪࠢࡠࠝࠢ࠹ࡦ ࠍട߃ࠆߣޔൻว‛3ߩᤨߩߺޔࡕ࡞ๆశଥᢙߩ⪺
ߒᷫዋ߇ࠄࠇߚޕߎߩߎߣ߆ࠄޔൻว‛3߇ൻ ว‛1,2ࠃࠅ߽ࡂࠗ࠼ࡠࡍ࡞ࠝࠠ࠰⒳ߩ↢ᚑ㊂߇ᄙ
ߎߣ߇ಽ߆ߞߚޕߎߩߎߣߪޔ㉄ൻ⸅ᇦᵴᕈᐨ
ߣኻᔕߒߡߚޕ
એߩߎߣ߆ࠄޔTi3⟎឵ࡐ㉄ႮߩA-Ti3ࠨࠗ
࠻߇ H2O2ࡌࠬߩ㉄ൻ⸅ᇦᔕߦ㜞ᵴᕈࠍ␜ߒޔ ߘࠇߪޔൻว‛3 ߣH2O2ߣߩᔕߢ↢ᚑߔࠆࡂࠗ
࠼ࡠࡍ࡞ࠝࠠ࠰⒳ߩ↢ᚑㅦᐲ߇ઁߩൻว‛ࠃࠅ߽ㅦ
ߎߣߦ࿃ߔࠆߣ⚿⺰ߒߚޕߐࠄߦޔX✢᭴ㅧ⸃
ᨆ࠺࠲߆ࠄ᳞ߚ㉄⚛ߩBond Valence Sumߪޔ O(1) 1.69, O(2) 1.73, O(3) 1.45, O(33) 1.75, O(39) 1.69, O(40) 1.72, O(41) 1.65, O(42) 1.67,O(43) 1.52 ߣߥߞߡޔ࿑3ߩA-Ti3ߩTi-O-Ti⚿ว㉄⚛(O(3)
ߣO(43))ߦࠆࡊࡠ࠻ࡦ߇ޔࠃࠅࠬࡓ࠭ߥࡂࠗ࠼
ࡠࡍ࡞ࠝࠠ࠰⒳ߩ↢ᚑࠍଦㅴߒߡࠆߎߣ߽⏕ߒ ߚޕ
ࠪࡦࠞ࠶ࡊࡦࠣࠍߒߚࠪࠞ㕙߳ߩࡐ
㉄Ⴎߩ࿕ቯൻԙ3,10)
ࡐ㉄Ⴎߩ࿕ቯൻᴺߣߒߡޔࠕࡒࡦၮࠍ߽ߟࠪࡦ
ࠞ࠶ࡊࡦࠣࠍߒߚࡐ㉄Ⴎߩ࿕ቯൻ߇ႎ๔ߐ ࠇߡࠆ߇ޔᵴᕈࠨࠗ࠻߳ߩࠕࡒࡦၮߩ㈩߇⸅ᇦ ᵴᕈߩૐਅࠍߊߎߣ߇ࠄ߆ߦߥߞߡࠆ11)ޕߘ ߎߢᧄ⎇ⓥߢߪޔࠕࡦࡕ࠾࠙ࡓࠞ࠴ࠝࡦࠍ߽ߟࠪ
ࡦࠞ࠶ࡊࡦࠣ((MeO)3Si(CH2)3N(CH3)3Cl)ࠍ↪
ߡޔࡐ㉄Ⴎߩ߽ߟ⽶㔚⩄ߣࠕࡦࡕ࠾࠙ࡓࠞ࠴ࠝ
ࡦߣߩ㕒㔚⊛⋧↪ࠍ↪ߔࠆߎߣߦࠃࠅޔࡐ
㉄Ⴎࠍࠪࠞ㕙ߦ࿕ቯൻߒޔᵴᕈὐߩ៊ᄬࠍ㒐ߋ ߎߣߦᚑഞߒߚ(ࠬࠠࡓ 1 ෳᾖ)ޕߎߎߢߪޔဋ৻
㉄ൻ⸅ᇦ♽ߢᵴᕈࠍ␜ߔ K4[PMo11VVO40] (PMoV) ࠍߦߒߡޔ࿕ቯൻ೨ᓟߩ㉄ൻᵴᕈߦߟߡᬌ⸛ߒ ߚޕ߹ߚޔ࿕ቯൻᓟߩࠠࡖࠢ࠲࡚ࠪࡦߣߒ ߡޔ࿕31P NMRޔDR UV-visޔTEMࠍⴕߞߚ⚿
ᨐޔࡐ㉄Ⴎߪࠪࠞ㕙ߦ㜞ಽᢔߒߡᜂᜬߒߡ
ࠆߎߣࠍ⏕ߒߚޕ
0 0.002 0.004 0.006 0.008 0.01 0.012
0 2 4 6 8 10
TOF/s-1
[H+]/POM 3
2 1
࿑2. ࠪࠢࡠࠝࠢ࠹ࡦߩࠛࡐࠠࠪൻᔕߦኻߔ ࠆࡊࡠ࠻ࡦᢙଐሽᕈ.
࿑3. ൻว‛3ߩ࠴࠲ࡦ(IV)ਃ⟎឵ࠨࠗ࠻ߩX✢⚿
᥏᭴ㅧ.
1. Ti⟎឵ࡐ㉄Ⴎࠍ⸅ᇦߣߒߚH2O2ߦࠃࠆࠕ࡞
ࠤࡦߩࠛࡐࠠࠪൻᔕa
ၮ⾰ (mmol) ⸅ᇦ TOFs-1b ㆬᛯ₸/%
ࠪࠢࡠࠝࠢ࠹ࡦ (7.70)
1 3.7 ´ 10-4 4.7´ 10-4c
> 99d
> 99d 2 1.2´ 10-3
1.3´ 10-3c
> 99d
> 99d
ࠪࠢࡠࡋࠠࡦ (4.93) 1-ࠝࠢ࠹ࡦ
(6.37)
3 12 31 23
4.8´ 10-3 3.6´ 10-3c
—e 7.6´ 10-6e 1.2´ 10-4e
—g 5.4´ 10-6g 3.1´ 10-5g
> 99d
> 99d
— 83f 86f
—
>99h
>99h
aReaction conditions: catalyst 0.02 mmol, substrates 4.93㧙7.70 mmol, 30 % H2O2 9.72 mmol, solvent, 1:1 (v/v) CH2Cl2/CH3CN 30 mL, under air. bTOF = turnover number (TON)/s after 5 min. cafter 1 h. dcyclooctene oxide was epoxidation product. eafter 4 h. fcyclohexene oxide and cyclohexanediol were epoxidation products.
gafter 3 h. h1,2-epoxyoctane was epoxidation product.
PMoV ࿕ቯൻࠪࠞ(PMoV-SiO2)ࠍ࿕⸅ᇦߣߒ ߚࠗ࠰ࡉ࠴࡞ࠕ࡞࠺ࡅ࠼ሽਅߢߩࠕ࡞ࠦ࡞ߩ㉄
ൻᔕ⚿ᨐࠍ2ߦ␜ߔޕ㉄ൻ↢ᚑ‛ߪޔߘࠇߙࠇ ࡌࡦ࠭ࠕ࡞࠺ࡅ࠼ޔࠝࠢ࠴࡞ࠕ࡞࠺ࡅ࠼ޔࠪࠢࡠࡋ
ࠠࠨࡁࡦߢޔㆬᛯ₸ߪ>99%ߢߞߚޕ࠲ࡦࠝ
ࡃᢙ(TON)ߪޔߕࠇߩ႐ว߽PMoVࠍ↪ߚဋ
৻♽ࠃࠅ߽ PMoV-SiO2ࠍ↪ߚਇဋ৻♽ߩ߶߁߇ 㜞߆ߞߚޕ߹ߚޔPMoVߣࠪࠞࠍනߦ‛ℂᷙวߒ
ߚ PMoV/SiO2ࠃࠅ߽ࠪࡦࠞ࠶ࡊࡦࠣࠍߒ
ߚ PMoV-SiO2 ߩ߶߁߇㜞ᵴᕈߢߞߚޕએߩߎ
ߣ߆ࠄޔ㕒㔚⊛ߦࡐ㉄Ⴎࠍ࿕ቯൻߔࠆߣޔᵴᕈὐ
᭴ㅧߩ៊ᄬߥߊࡐ㉄Ⴎࠍ࿕ቯൻߢ߈ࠆߎߣ߇ಽ ߆ߞߚޕ
࠽ࡁ⚦ሹࠍ߽ߟࠪࠢࡠࡋࠠࠨࡦࠫࠞ࡞ࡏࡦ㉄㌃(II)
㍲ࠍ࿕⸅ᇦߣߒߚࠕ࡞ࠦ࡞ߩ㉄ൻ߅ࠃ߮ਇ ဋ৻♽㉄ൻ⸅ᇦᔕਛߩᵴᕈ㉄⚛⒳ߩන㔌߅ࠃ߮
᭴ㅧ⸃ᨆԚ4)
[CuII,II2(OOCC6H10COO)2]·H2O(4)ࠍ࿕⸅ᇦߣߒ ߚㆊ㉄ൻ᳓⚛ߦࠃࠆ⒳ޘߩࠕ࡞ࠦ࡞ߩ㉄ൻᔕ⚿
ᨐࠍ3ߦ␜ߔޕᧄᔕਛߩ⸅ᇦߩ⁁ᘒߪㆊ㉄ൻ᳓
⚛ߩỚᐲߦ⪺ߒߊଐሽߒߡ߅ࠅޔ㌃1ේሶߦኻߒߡ 46એਅߩH2O2ࠍᷝടߒߚ႐วޔ⸅ᇦߩ⦡߇㕍⦡
߆ࠄ✛⦡ߦᄌ⦡ߒߚߩߦኻߒޔ69એߩᷝട㊂ߩ ႐วߪޔ㕍⦡߆ࠄ⨥⦡߳ߣᄌ⦡ߒߚޕTOF ߪޔH2O2
ᷝട㊂ߩჇടߣߣ߽ߦ߽㜞ߊߥߞߚޕᔕਛߦ᷹ⷰ
ߐࠇߚ⸅ᇦߩ⦡ߩᄌൻ(✛⦡߽ߒߊߪ⨥⦡)߇㕍⦡ߦ ᚯߞߡߒ߹߁ߣޔ⸅ᇦᔕ߽ㅴⴕߒߥߊߥߞߚߎߣ ߆ࠄޔߎߩ✛⦡߽ߒߊߪ⨥⦡ߩൻቇ⒳߇ᔕਛ㑆
ߢࠆߣផኤߒߚޕߐࠄߦޔൻว‛4ߪߕࠇߩၮ
⾰ߦኻߒߡ߽㉄ൻ⸅ᇦᵴᕈࠍ␜ߒߚ߇ޔಽሶࠨࠗ࠭
ߩᲧセ⊛ዊߐ 2-ࡊࡠࡄࡁ࡞ߩ߶߁߇ࡌࡦࠫ࡞
ࠕ࡞ࠦ࡞߿ࠪࠢࡠࡋࠠࠨࡁ࡞ߥߤߩᄢ߈ߩၮ
⾰ࠃࠅ߽TOF߇㜞߆ߞߚߎߣߪޔൻว‛4ߩ߽ߟ5 Έ⒟ᐲߩ࠽ࡁ⚦ሹߩᒻ⁁ㆬᛯᕈߦࠃࠆ߽ߩߣᕁࠊࠇ ࠆޕ߹ߚޔ࠽ࡁ⚦ሹࠍ߽ߚߥ㌃⸅ᇦߢߪᵴᕈࠍ␜
ߐߥ߆ߞߚߎߣ߆ࠄޔᧄ㍲ߩ߽ߟ࠽ࡁ⚦ሹ߇⸅ᇦ ᵴᕈߩะߦലᨐ߇ࠆߎߣ߇ಽ߆ߞߚޕߐࠄߦޔ ᧄᔕߪቢోߥਇဋ৻♽ᔕߢㅴⴕߒߡ߅ࠅޔ⸅ᇦ ߩᔕṁᶧ߳ߩᨴߺߒߪߥߊޔ⸅ᇦ߽ഠൻߒߡ
ߥߎߣࠍ⏕ߒߚޕ
⛯ߡޔᔕਛ㑆ߣ⠨߃ࠄࠇࠆ✛⦡߽ߒߊߪ⨥
⦡ߩൻቇ⒳ߩ߁ߜޔ✛⦡ߩൻቇ⒳ߩන㔌ࠍ⹜ߺߚޕ
✛⦡ߩ㌃(II)-ࡍ࡞ࠝࠠ࠰⒳ (H2[Cu2II,II(OOCC6H10- COO)2(O2)]×H2O(5))ߪޔࠕ࠻࠾࠻࡞ਛߢൻว‛
4ߦ20ߩH2O2ࠍᷝടߔࠆߎߣߢන㔌ߔࠆߎߣ߇
᧪ߚޕൻว‛ 4 ߣ5 ߩ☳ᧃ X ✢࿁᛬࠺࠲߆ࠄ
࠻ࡌ࡞࠻⸃ᨆߦࠃࠅߘߩ᭴ㅧࠍቯߔࠆߣޔൻ ว‛ 4 ߩ 2 ᰴరߩ[Cu2(OOC6H10COO)]ጀ㑆ߦޔ m-1,2-transဳߩࡍ࡞ࠝࠠ࠰⒳߇᨞ᯅߒߡ߅ࠅޔߘࠇ ߦࠃߞߡጀ㑆ߩ Cu-Cu㑆ߩ〒㔌߇2.992(6) Å߆ࠄ 4.572(4) Åߦ㐳ߊߥߞߡࠆߎߣ߇ಽ߆ߞߚ (࿑4)ޕ ߐࠄߦޔൻว‛ 5 ߩࡑࡦࠬࡍࠢ࠻࡞ߢߪޔ805 cm-1ߦᣂߚߥࡃࡦ࠼߇᷹ⷰߐࠇߚ (࿑5)ޕߎߩࡃࡦ
࠼ߪޔ760 cm-1ઃㄭߦ᷹ⷰߐࠇࠆࠨࠗ࠼-ࠝࡦဳߩ
SiO2 OO
O OO O
Si (H3C)3+N
Si (H3C)3+N
OO
O OOO
Si (H3C)3+N
Si (H3C)3+N
4KCl Cl-
Cl- Cl-
Cl-
4-
SiO2 OO
O OO O
Si (H3C)3+N
Si (H3C)3+N
OO
O OOO
Si N+(CH3)3
Si N+(CH3)3
4-
Scheme 1.
2. PMoV࿕ቯൻࠪࠞࠍ⸅ᇦߣߒߚಽሶ⁁㉄⚛
ߦࠃࠆࠕ࡞ࠦ࡞ߩ㉄ൻa
(mmol)ၮ⾰ ⸅ᇦ TONb
ࡌࡦࠫ࡞ࠕ࡞ࠦ࡞ PMoV 54
(48.4) PMoV-SiO2 153
PMoV/SiO2c 21
PMoV-SiO2d 152
1-ࠝࠢ࠲ࡁ࡞ PMoV 22
(6.34) PMoV-SiO2 117
ࠪࠢࡠࡋࠠࠨࡁ࡞
(9.40)
PMoV
PMoV-SiO2e 21 84
aReaction conditions: PMoV 20 mmol, PMoV-SiO2
(0.082 mmol/g, 5 mmol of PMoV), CH3CN 3 – 8 mL, alcohol 6.34 – 48.4 mmol, IBA 11.0 – 37.6 mmol, P(O2)
= 1 atm, reaction temperature 85 ºC. bTurnover number (TON) after 168 h. cPMoV/SiO2 (0.082 mmol/g, 5mmol of PMoV) was used. dWater (5 mL) was used as a solvent. ePMoV-SiO2 (0.057 mmol/g, 5 mmol of PMoV) was used.
3. ࠪࠢࡠࡋࠠࠨࡦࠫࠞ࡞ࡏ㉄㌃(II)㍲ࠍ⸅ᇦ ߣߒߚㆊ㉄ൻ᳓⚛ߦࠃࠆࠕ࡞ࠦ࡞ߩ㉄ൻa
ၮ⾰ (mmol) ㆬᛯ₸/%b TOFs-1c
2-ࡊࡠࡄࡁ࡞
(13.1)
ࠕ࠻ࡦ (>99) 1.6 ´ 10-3 2-ࡊࡠࡄࡁ࡞
(13.1)d
ࠕ࠻ࡦ (>99) 5.8 ´ 10-3
ࠪࠢࡠࡋࠠࠨࡁ࡞
(9.5)e ࠪࠢࡠࡋࠠࠨࡁࡦ
(>99)
1.1´ 10-4
ࠪࠢࡠࡋࠢࠨࡁ࡞
(9.5)d ࠪࠢࡠࡋࠠࠨࡁࡦ
(>99)
1.6´ 10-4 ࡌࡦࠫ࡞ࠕ࡞ࠦ࡞
(9.7) ࡌࡦ࠭ࠕ࡞࠺ࡅ࠼
(>99)
7.0´ 10-4 ࡌࡦࠫ࡞ࠕ࡞ࠦ࡞
(9.7)d ࡌࡦ࠭ࠕ࡞࠺ࡅ࠼
(>99)
1.5´ 10-3
1-ࠝࠢ࠲ࡁ࡞
(6.4) ࠝࠢ࠴࡞ࠕ࡞࠺ࡅ࠼
(>99)
1.1´ 10-4
1-ࠝࠢ࠲ࡁ࡞
(6.4)d
ࠝࠢ࠴࡞ࠕ࡞࠺ࡅ࠼
(>99)
1.6´ 10-4
aReaction conditions: catalyst 206 mmol, substrate 6.4 – 13.1 mmol, 30 % H2O2 9.7 mmol (23-fold excess), CH3CN 10 mL. bafter 1 h. cTOF = turnover number (TON)/s after 1 h. dH2O2 (48.5 mmol, 113-fold excess) was used. eH2O2 (19.4 mmol, 46-fold excess) was used.
CuII-OO-CuII ⒳ ߿ 590–616 cm-1 ߦⷰ ᷹ߐ ࠇ ࠆ CuIII(m2-O)2CuIII ⒳ ߩ ߽ ߩ ߣ ߪ⇣ߥ ߞ ߡ߅ࠅ ޔ 800–840 cm-1 ߦ ⷰ ᷹ ߐ ࠇ ࠆ m-1,2-trans CuII-OO-CuII⒳ߩ O-O ᝄേߦࠃࠆ߽ߩߣኻᔕߒߡ
ߚޕߐࠄߦᾲಽᨆ߆ࠄޔൻว‛5ਛߩࡍ࡞ࠝࠠ࠰
⒳ߪ133͠߹ߢቯߢࠆߎߣ߽⏕ߒߚޕߎߩࠃ ߁ߥ㌃-ࡍ࡞ࠝࠠ࠰⒳ߪޔ↢㉂⚛㘃ૃࡕ࠺࡞㍲ߢ ߪᣢߦႎ๔ߐࠇߡࠆ߽ߩߩޔ࿕⸅ᇦ߆ࠄන㔌
᭴ㅧ⸃ᨆߐࠇߚߪߥޕ߹ߚޔ100͠એߩ㜞
ᾲ⊛ቯᕈࠍ␜ߔ㌃(II)-ࡍ࡞ࠝࠠ࠰⒳ߣ߁߽ߩ߽
ߎࠇ߹ߢߦႎ๔߇ߥߎߣ߆ࠄޔ㜞ಽሶ㍲߇ࠬ
࠲࠶ࠠࡦࠣߔࠆߎߣߦࠃߞߡ࠽ࡁ⚦ሹࠍ᭴▽ߒߡ
ࠆᧄ⸅ᇦߩࠃ߁ߥᯏ-ήᯏࡂࠗࡉ࠶࠼᧚ᢱ߇ޔߎ ߩ․⇣ߥേࠍᒁ߈ߎߒߡࠆߣ⠨߃ߡࠆޕ ᦨᓟߦޔᓧࠄࠇߚ㌃(II)ࡍ࡞ࠝࠠ࠰⒳߇㉄ൻᵴᕈߩ
ࠆᔕਛ㑆ߢࠆ߆ߤ߁߆ࠍ⏕ߔࠆߚޔ NMR▤ਛߢൻว‛5ߣ2-ࡊࡠࡄࡁ࡞ࠍᔕߐߖ ߚޕߘߩ⚿ᨐޔH2O2߇ሽߒߥߊߡ߽ࠕ࠻ࡦࠍ↢
⒳ߩ৻ߟߢࠆߎߣࠍ⏕ߒߚޕ߽߁৻ߟߩ⨥⦡ߩ ਛ㑆ߦߟߡߪޔ߹ߛන㔌ߦᚑഞߒߡߥ߇ޔ
ᓟޔวᚑ᧦ઙࠍᬌ⸛ߒߡන㔌᭴ㅧ⸃ᨆࠍ⋡ᜰߔ
੍ቯߢࠆޕ
⚿⺰
ㅀߩࠃ߁ߦޔਥߣߒߡ3ߟߩ⎇ⓥ࠹ࡑࠍㆀⴕߔ ࠆߎߣߦࠃࠅޔ㉄ൻ⸅ᇦߩಽሶ⸳⸘ߦ㑐ߔࠆၮ␆⊛
ߥ⍮߇ᓧࠄࠇߚޕᓟߪޔߎࠇࠄߩ⍮ࠍࡌࠬ
ߦޔⅣႺ㗴߳ߩ⸃ߦะߌߚ㉄ൻ⸅ᇦߩ㐿⊒ࠍ⋡
ᜰߔ੍ቯߢࠆޕ
⻢ㄉ
ᧄ⎇ⓥߪޔ2004-2005ᐕᐲᄹᎹᄢቇห⎇ⓥᅑബ ഥᚑߩ߽ߣߦⴕࠊࠇߚޕ߹ߚޔᧄ⎇ⓥߩ৻ㇱߪޔᢥ ㇱ⑼ቇ⋭ߩ⑼ቇ⎇ⓥ⾌ഥ㊄(16750126)ߩេഥࠍ ฃߌߡⴕࠊࠇߚޕ
ᢥ₂
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Synthesis, characterization, and catalysis of H2O2- based thioether oxidation. Inorg. Chem.39:3828-3837.
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(a) (b)
࿑4.aゲ߆ࠄߚ4ߩಽሶ᭴ㅧ(a)ޔaゲ߆ࠄߚ 5ߩ ಽሶ᭴ㅧ(b).
Raman shift/cm-1 (b)
(a)
771
805
814 771
࿑5. ൻว‛4(a)߅ࠃ߮ൻว‛ 5(b)ߩࡑࡦࠬࡍࠢ
࠻࡞.
structure of the dimeric, Ti-O-Ti bridged anhydride form K10H2[a,a-P2W18Ti6O77]·17H2O and conforma- tion of dimeric forms in aqueous solution by ultra- centrifugation molecular-weight measurements.
Dalton Trans. 2872-2878.
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11) Johnson BJS and Stein A (2001) Surface modifica- tion of mesoporous, macroporous, and amorphous silica with catalytically active polyoxometalate clusters.Inorg. Chem.40: 801-808.