ᅛᐃ໬Pd㘒య-᭷ᶵศᏊゐ፹ࡢXAFS࡟ࡼࡿᵓ㐀ゎᯒ࡜࢔ࣜࣝ໬཯ᛂᶵᵓࡢゎ᫂ᮏ಴ ೺ᮾிᕤᴗ኱Ꮫ
1. ࡣࡌࡵ࡟ ᅛయ⾲㠃࡬」ᩘࡢάᛶⅬࢆᑟධࡍࡿࡇ࡜࡛ࠊࡑࢀࡽάᛶⅬࡢ༠ዌⓗゐ፹స⏝࡟ࡼࡿ໬Ꮫ཯ᛂࡢ኱ᖜ࡞ಁ㐍ࡀྍ⬟࡜࡞ࡿ[1]ࠋ౛࠼ࡤࠊPd 㘒య࡜᭷ᶵሷᇶࡢ୧᪉ࢆྠ୍⾲㠃࡟ᅛᐃࡋࡓゐ፹ࢆ⏝࠸ࡿ࡜ࠊ་⸆ရ࣭⢭ᐦ໬Ꮫရྜᡂ࡟࠾࠸࡚㔜せ࡞ồ᰾๣ࡢ࢔ࣜࣝ໬཯ᛂࡀ
኱ᖜ࡟ಁ㐍ࡉࢀࡿ[2]ࠋࡇࢀࡣࠊPd 㘒యࡀ࢔ࣜࣝ໬๣ࢆࠊ
᭷ᶵሷᇶࡀồ᰾๣ࢆࡑࢀࡒࢀάᛶ໬ࡍࡿࡓࡵ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞༠ዌⓗゐ፹స⏝ࡢⓎ⌧ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿ࡟ࡣࠊᅛయ⾲㠃࡟Ꮡᅾࡍࡿ Pd 㘒యࡢヲ⣽࡞ᵓ㐀࣭Pd 㘒య࡜ྠ୍⾲㠃࡟Ꮡᅾࡍࡿ᭷ᶵศᏊ࡜
ࡢ┦஫స⏝࣭ᇶ㉁ศᏊ࡜ࡢ཯ᛂ࡟ࡼࡿ Pd 㘒యࡢᵓ㐀ኚ໬࡜཯ᛂᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿᚲせࡀ࠶ࡿࠋࡇࢀࡽࡢ⫼ᬒ࡟ᇶ࡙ࡁࠊ➹⪅ࡽࡣ⊂⮬࡟㛤Ⓨࡋࡓࢩࣜ࢝ᅛᐃ໬ Pd ࣅࢫ࣍ࢫࣇ࢕ࣥ㘒య (PP-Pd)㸫᭷ᶵሷ
ᇶ 1,4-diazabicyclo[2.2.2]octane (DABCO) ゐ ፹(SiO2/DABCO/PP-Pd) ࡢ XAFS ࡟ࡼࡿヲ⣽ᵓ㐀ゎᯒ

Scheme 1. SiO2/DABCO/PP-Pd ࡢㄪ〇࡜ᅛᐃ໬ Pd 㘒࡜཯ᛂᶵᵓゎ᫂ࢆ┠ⓗ࡜ࡋ࡚◊✲ࢆ⾜ࡗࡓ[3]ࠋయࡢᵓ㐀2. ⤖ᯝ࡜⪃ᐹࢆ⾲ 1 ࡟ࡲ࡜ࡵࡿࠋSiO2/DABCO/PP-Pd ௨እࡢゐ2-1 ࢩࣜ࢝ᅛᐃ໬ Pd 㘒యࡢㄪ〇

፹࡛ࡣࠊPd ࡜ Cl ࡣ㏆࠸್ࢆ♧ࡋ࡚࠾ࡾࠊ๓㥑య㘒 SiO2/DABCO/PP-Pd ࡢㄪ〇ἲࢆ Scheme 1 ࡟♧యࡢᏑᅾࡀᨭᣢࡉࢀࡿࠋDABCO ࢆᅛᐃࡍࡿ࡜ࠊPdࡍࠋࢡࣟࣟࣉࣟࣆࣝᇶ࡜ࡢᅄ⣭໬཯ᛂ࡟ࡼࡗ࡚࡟ᑐࡍࡿሷ⣲࠾ࡼࡧ❅⣲㔞ࡢቑຍࡀ☜ㄆࡉࢀࡓࠋDABCO ࢆ SiO2 ⾲㠃࡟ᅛᐃࡋࡓᚋࠊࢩࣛࣥ࢝ࢵࣉ ⥆࠸࡚ࠊᅛᐃ໬᭷ᶵศᏊࡢ໬Ꮫᵓ㐀ࢆ☜ㄆࡍࡿࡓࣜࣥࢢ཯ᛂ࡟ࡼࡗ࡚ PP-Pd 㘒యࢆᑟධࡋࡓࠋゐ፹ᵓࡵࠊᅛయ NMR ࠾ࡼࡧ XPS㐀࣭ゐ፹άᛶࢆẚ㍑ࡍࡿࡓࡵ࡟ࠊPP-Pd ࡢࡳࢆᅛᐃCP/MAS NMR

ࡋࡓゐ፹ (SiO2/PP-Pd)ࠊDABCO ࡢ௦ࢃࡾ࡟࣓ࢳDABCOࠊ࣓ࢳࣝᇶࠊ࠾ࡼࡧ࣊࢟ࢩࣝᇶࡀᏑᅾࡋ࡚ࣝᇶࡶࡋࡃࡣ࣊࢟ࢩࣝᇶࢆᅛᐃࡋࡓゐ፹࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡉࡽ࡟ࠊPP-Pd 㘒య⏤᮶ࡢࣇ

(SiO2/Me/PP-Pd, SiO2/Hex/PP-Pd) ࡶྜࢃࡏ࡚ㄪ࢙ࢽࣝᇶࡶ☜ㄆࡉࢀࡓࠋ31P MAS NMR〇ࡋࡓࠋࡍ࡭࡚ࡢࢧࣥࣉࣝ࡟࠾࠸࡚ࠊ0 ppm ௜㏆࡟ᙉ࠸ࢩࢢ

ᐃࢆ⾜ࡗࡓࠋᅛయ 13Cᐃࡢ⤖ᯝࠊࡑࢀࡒࢀࡢゐ፹୰࡟ᐃ࡛ࡣࠊࢼࣝࡀほ ࡉࢀࡓࠋࡇࡢ⤖ᯝࡣࠊᅛᐃ໬ᚋࡶࣅࢫ࣍2-2 ࢩࣜ࢝ᅛᐃ໬ Pd 㘒యࡢᵓ㐀ゎᯒࢫࣇ࢕ࣥ㓄఩Ꮚࡀ Pd ࡬㓄఩ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚ ㄪ〇ࡋࡓᅛᐃ໬ Pd 㘒య࡟ྵࡲࢀࡿ Pd ࠾ࡼࡧሷ࠸ࡿࠋXPS⣲࣭Ⅳ⣲࣭❅⣲㔞ࢆඖ⣲ศᯒ࡟ࡼࡗ࡚ồࡵࡓࠋ⤖ᯝࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋຍ࠼࡚ࠊN1s ࡟⏤᮶ࡍᐃ࡟࠾࠸࡚ࠊPd ࡣ 2 ౯ࡢ≧ែ࡛Ꮡᅾ⾲ 1. ྛࢧࣥࣉࣝࡢඖ⣲ศᯒ⤖ᯝelement / mmol g-1
CNClPdSiO2/DABCO/PP-Pd 11.5

1.1

0.7

0.17

SiO2/PP-Pd

11.9

0.4

0.3

0.28

SiO2/Me/PP-Pd

9.6

0.3

0.3

0.18

SiO2/Hex/PP-Pd

10.8

0.3

0.3

0.25(j)(i)
Normalized Absorption / a.u.

sampleࡿࢩࢢࢼࣝࡀSiO2/DABCO/PP-Pd࡛ࡣ399.6 eV࠾ࡼࡧ 402 eV ࡟ 2 ✀㢮ほ ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣࠊ୕⣭࠾ࡼࡧᅄ⣭໬ࡉࢀࡓ࢔࣑ࣀᇶࡢ୧᪉ࡀᏑᅾࡋ࡚࠸

(h)(g)(f)(e)(d)ࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊDABCO ࡀᅄ⣭໬ࡉࢀࡓ≧ែ࡛ᅛᐃࡉࢀ࡚࠸ࡿࡇ࡜ࢆᨭᣢࡋ࡚࠸ࡿࠋ(c) ⥆࠸࡚ࠊᅛᐃ໬ Pd 㘒యࡢᵓ㐀ࢆࡼࡾヲ⣽࡟Ỵᐃ

(b)

ࡍࡿࡓࡵࠊ
Pd K-edge XAFSᐃࢆSAGA-LS BL07(a)࡟࡚⾜ࡗࡓࠋࡑࢀࡒࢀࡢࢧࣥࣉࣝࡢ࠾ࡼࡧ๓㥑య

24.30

24.32

PP-Pd㘒య⁐ᾮࡢXANES ࢫ࣌ࢡࢺࣝࢆᅗ1 ࡟♧ࡍࠋ

24.34

24.36

24.38 24.40x103

Photon Energy / keVᅛᐃ໬㘒యࡢࢫ࣌ࢡࢺࣝࡣࠊࣜࣇ࢓ࣞࣥࢫ࡜ࡋ࡚

ᅗ 1. Pd K-edge XANES ࢫ࣌ࢡࢺࣝ: (a) SiO2/PP-Pd,

ᐃࡋࡓ PdO ࡸ Pd foil ࡜඲ࡃ␗࡞ࡾࠊPdCl2(PPh3)2(b) SiO2/DABCO/PP-Pd, (c) SiO2/Me/PP-Pd, (d)࡜ẚ㍑ⓗ㢮ఝࡋ࡚࠸ࡿࠋࡉࡽ࡟ࠊ๓㥑య PP-Pd ࡜ࡢ

SiO2/Hex/PP-Pd, (e) PP-Pd ࡢ THF ⁐ ᾮ , (f)ẚ㍑࡛ࡣࠊᅛᐃ໬࡟ࡼࡿ XANES ࢫ࣌ࢡࢺࣝࡢኚ໬PdIICl2(PPh3)2, (g) [PdIICl(K3-allyl)]2, (h) Pd0(PPh3)4,ࡣ࡯࡜ࢇ࡝ほ ࡉࢀࡎࠊ๓㥑య㘒యࡢᵓ㐀ࢆ⥔ᣢࡋ(i) Pd0 foil, (j) PdIIO.

ࡓࡲࡲᅛᐃࡉࢀ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ⥆࠸࡚ࠊྛ4ࢧࣥࣉࣝࡢ EXAFS ࢫ࣌ࢡࢺࣝࢆᅗ 2 ࡟ࠊEXAFS
ࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝࢆᅗ 3 ࡟♧ࡍࠋᅗ 2 ࡼࡾࠊࡍ࡭࡚ࡢࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࠊ఩┦ࡀ࡯ࡰ᏶඲࡟୍k3 Ȥ(k) / Å-3ᅛᐃ໬๓ᚋࡸඹᏑᅛᐃࡋࡓ᭷ᶵศᏊࡢ✀㢮࡟ࡼࡽࡎ

20⮴ࡋ࡚࠸ࡓࠋᅛᐃ໬࡟ࡼࡿ Pd 㘒య୰ᚰᵓ㐀ࡢኚ໬ࡀ࡯࡜ࢇ࡝࡞࠸ࡇ࡜ࡀࠊࡇࡢ⤖ᯝ࠿ࡽࡶ♧ࡉࢀࡓࠋᅗ 3 ࠿ࡽࡣࠊㄪ〇ࡋࡓゐ፹ࡀ Pd-P ࠾ࡼࡧ Pd-Cl(Pd-P/Cl) ⤖ྜࢆ᭷ࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡑ

-2-402468k / Å-1

101214ࡇ࡛ࠊࡇࡢࣆ࣮ࢡ࡟㛵ࡋ࡚࣮࢝ࣈࣇ࢕ࢵࢸ࢕ࣥࢢゎᅗ2. EXAFS ࢫ࣌ࢡࢺࣝ㸸SiO2/DABCO/PP-Pd (㉥Ⅼ),ᯒࢆ⾜ࡗࡓࠋ⤖ᯝࢆ⾲ 2 ࡟ࡲ࡜ࡵࡿࠋࡍ࡭࡚ࡢࢧࣥ

SiO2/PP-Pd ( ㉥ ⥺ ), SiO2/Me/PP-Pd ( 㯮 ⥺ ),ࣉࣝ࡟࠾࠸࡚ࠊPd-P/Cl ⤖ྜࡢᖹᆒ㓄఩ᩘࡣ 3 ௜㏆ࠊ

SiO2/Hex/PP-Pd (㯮Ⅼ), PP-Pd ࡢ THF ⁐ᾮ (㟷⥺).

⤖ྜ㊥㞳ࡣ 2.26~2.27 Å ࡜࡞ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊPd㘒యࡀ஧ࡘࡢPཎᏊ࠾ࡼࡧ୍ࡘࡢClཎᏊࢆ᭷ࡋ࡚࠸ࡓࡵࠊࡇࡢ DW ᅉᏊࡢቑຍࡣ⤖ྜࡢ⇕᣺ື࡟⏤᮶ࡍࡿ᝿ᐃᵓ㐀࡜୍⮴ࡋ࡚࠸ࡿࠋ୍᪉࡛ࠊDW ᅉᏊ࡟㛵ࡿࡶࡢ࡛ࡣ࡞ࡃࠊ㘒య㦵᱁ࡢṍࡳ࡟㉳ᅉࡍࡿ࡜᥎ᐃ

ࡋ࡚ࡣࠊPd 㘒య࡜ඹᏑᅛᐃࡍࡿ᭷ᶵศᏊࡢࢧ࢖ࢬࡉࢀࡿࠋࡍ࡞ࢃࡕࠊඹᏑᅛᐃࡉࢀࡓ᭷ᶵศᏊࡣ SiO2ࡀ኱ࡁࡃ࡞ࡿ࡯࡝ࠊቑຍࡍࡿഴྥࡀぢࡽࢀࡓࠋࡍ࡭⾲㠃࡟࡚ Pd 㘒య࡜㏆᥋ࡋ࡚Ꮡᅾࡋ࡚࠾ࡾࠊྠ᫬࡟࡚ࡢࢧࣥࣉࣝ࡟࠾࠸࡚⤖ྜ㊥㞳ࡣ࡯ࡰ୍⮴ࡋ࡚࠸ࡿゐ፹཯ᛂ࡬㛵୚࡛ࡁࡿྍ⬟ᛶࡀᴟࡵ࡚㧗࠸ࠋ཯ᛂࢆ⾜ࡗࡓ⤖ᯝࢆᘧ(1)࡟♧ࡍࠋDABCO ࢆඹᏑᅛᐃࡍࡿࡇ࡜࡛ゐ፹ᅇ㌿ᩘ (TON) ࡢྥୖࡀ☜ㄆࡉࢀ100(k)

ࡓࠋࡇࢀࡣࠊPd 㘒య࡟㏆᥋ࡋࡓ DABCO ࡀሷᇶゐ፹࡜ࡋ࡚ࡣࡓࡽࡁࠊethyl 3-oxobutanate ࢆάᛶ໬ࡍ

㽢㻜㻚㻟

(j)

ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ཯ᛂ᮲௳ࡢࡉࡽ࡞ࡿᨵⰋ࡟

(i)

80

ࡼࡗ࡚ࠊTON ࡣ᭱኱࡛ 100000 ࢆ㉸࠼ࠊ᪤Ꮡࡢ Pd

Pd-Cl

FT of k3 Ȥ(k)ゐ፹ࢆ෽㥙ࡍࡿ㧗άᛶࢆ♧ࡍࡇ࡜ࡶࢃ࠿ࡗࡓࠋ(h)60

Pd-C(g)Pd-P/Cl(f)40

Pd-P/Cl(e)(d)
20ࡉࡽ࡟ࠊ཯ᛂᚋࡢゐ፹ࢆᅇ཰ࡋࠊEXAFS(c)⾜ࡗࡓ࡜ࡇࢁࠊPd-P/Cl 㓄఩ᩘࡀ཯ᛂ๓ࡢ 3.0±0.5(b)࠿ࡽ 2.2±0.3 ࡟పୗࡋ࡚࠸ࡓࠋࡇࡢ⤖ᯝࡣࠊCl ࡢ⬺

(a)00

ᐃࢆ

123r/Å45㞳࡟ࡼࡿࠊ࢔ࣜࣝ໬཯ᛂࡢάᛶ✀࡛࠶ࡿ Ǒ-࢔ࣜࣝ6Pd ࡀ⏕ᡂࡍࡿ཯ᛂᶵᵓࢆᨭᣢࡋ࡚࠸ࡿࠋ

ᅗ 3. Pd K-edge EXAFS ࣇ࣮࢚ࣜኚ᥮ࢫ࣌ࢡࢺࣝ: (a)SiO2/PP-Pd,(b)SiO2/DABCO/PP-Pd,(c)3. ࡲ࡜ࡵ

SiO2/Me/PP-Pd, (d) SiO2/Hex/PP-Pd, (e) PP-Pd ࡢPd 㘒య࡜ DABCO ࢆ SiO2 ⾲㠃࡟ඹᏑᅛᐃࡍࡿࡇ

THF ⁐ᾮ, (f) PdIICl2(PPh3)2, (g) [PdIICl(K3-allyl)]2, (h)࡜࡛ࠊ࢔ࣜࣝ໬཯ᛂ࡟㧗άᛶࢆ♧ࡍゐ፹ࢆ㛤Ⓨࡋࡓࠋ

PdIICl2, (i) Pd0(PPh3)4, (j) Pd0 foil, (k) PdIIO.

ࡇࡢゐ፹ࡢヲ⣽ᵓ㐀࡜཯ᛂᶵᵓࢆ SAGA-LS BL07 ࡟࠾ࡅࡿ XAFS⾲ 2. EXAFS ࢫ࣌ࢡࢺࣝࡢ CF ゎᯒ⤖ᯝ a࡟㛵ࡍࡿᴟࡵ࡚㔜せ࡞▱ぢࡀᚓࡽࢀࡓࠋrc

¨ı2 d

¨E

ㅰ㎡㸸ᮏ◊✲ࡣ⛉Ꮫ◊✲㈝⿵ຓ㔠 (Grant No.

(Å)(Å2×10–3)(eV)26105003, 15H04182) ࡢᨭ᥼ࢆᚓ࡚⾜ࢃࢀࡲࡋࡓࠋ

2.6

2.26

2.80

–2.07

±0.4

±0.01±0.20

±2.03

2.6

2.27

3.63

–6.81

±0.4

±0.01

±0.20

±2.09

2.9

2.27

4.86

–3.11

±0.4±0.01±0.20±2.00

SiO2/DABCO/

3.0

2.265.05

–0.61

PP-Pd

±0.5±0.01

±0.20

±1.98

SampleSiO2/PP-Pd
SiO2/Me/PP-Pd
SiO2/Hex/PP-PdaNbᐃ࡟ࡼࡗ࡚ゎ᫂ࡋࠊ㧗άᛶⓎ⌧ࡢせᅉ¨k = 2.8 ~ 15 Å-1, ¨r = 1.4 ~ 2.2 Å , Shell: Pd-P/Cl, Rf:1.3~3.1%. b ᖹᆒ㓄఩ᩘ. c ⤖ྜ㊥㞳. dDW ᅉᏊ.
2-3 ࢩࣜ࢝ᅛᐃ໬ Pd 㘒య࡟ࡼࡿ࢔ࣜࣝ໬཯ᛂ
 ethyl 3-oxobutanate ࡜allyl methyl carbonate ࡢཧ⪃ᩥ⊩[1] K. Motokura, “Development of Multi-ActiveSite Catalysts for Surface Concerted Catalysis
Aimed at One-Pot Synthesis”, Bull. Chem. Soc. Jpn.
(2017) in press (doi:10.1246/bcsj.20160291).
[2] H. Noda, K. Motokura, et al., “HeterogeneousSynergistic Catalysis of a Pd Complex and anAmine on a Silica Surface for Acceleration of theTsuji-Trost Reaction”, Angew. Chem., Int. Ed., 51,8017 (2012)[3]  K. Motokura, et al., “A Pd-BisphosphineComplex and Organic Functionalities ImmobilizedontheSame
SiO2
Surface:
DetailedCharacterization and Its Use as an Efficient
Catalyst for Allylation”, Catal. Sci. Technol., 6, 5380
(2016).