ᅛᐃ໬㘒యゐ፹ࡢ ;$)6 ࡟ࡼࡿᵓ㐀ゎᯒ࡜༠ྠゐ፹స⏝ࡢゎ᫂ᮏ಴ ೺ᮾிᕤᴗ኱Ꮫ ≀㉁⌮ᕤᏛ㝔 ᛂ⏝໬Ꮫ⣔ 」ᩘࡢゐ፹άᛶⅬࢆᑟධࡋࡓᅛయ⾲㠃࡟࠾࠸࡚ࠊࡑࢀࡽάᛶⅬࡀ༠ዌⓗ࡟ᇶ㉁ศᏊࢆάᛶ໬
ࡋࠊゐ፹཯ᛂࡢ㏿ᗘࢆ኱ᖜ࡟ྥୖࡉࡏࡿࠕ୙ᆒ୍⣔༠ྠゐ፹స⏝ࠖࡀὀ┠ࢆ㞟ࡵ࡚࠸ࡿࠋᮏ◊✲࡛ࡣࠊࢩࣜ࢝⾲㠃࡟ Rh ࠶ࡿ࠸ࡣ Pd 㘒య࡜᭷ᶵሷᇶࢆᅛᐃࡋࡓゐ፹ࢆㄪ〇ࡋࡓࠋㄪ〇ࡋࡓゐ፹ࡢᵓ㐀ࢆ XAFSᐃ➼ࡢศගᏛⓗᡭἲࢆ⏝࠸࡚᫂ࡽ࠿ࡋࠊ༠ྠゐ፹స⏝ࡢゎ᫂ࢆヨࡳࡓࠋRh 㘒య࡜➨୕⣭࢔࣑ࣀᇶࢆᅛᐃࡋࡓࢩࣜ࢝ࢆ⏝࠸ࡿ࡜ࠊࣇ࢙ࢽࣝ࣍࢘㓟ࡢ 1,4-௜ຍ཯ᛂ࡟࠾ࡅࡿゐ፹άᛶࡀࠊྠ୍⾲㠃࡟➨୕⣭࢔࣑ࣀᇶࡀᏑᅾࡋ࡞࠸ሙྜ࡜ẚ㍑ࡋ࡚ࠊ኱ᖜ࡟ྥୖࡋࡓ[1]ࠋ
࢔࣑ࣀᇶࡢᏑᅾ࡟ࡼࡿ Rh 㘒యࡢᵓ㐀ኚ໬ࡢ᭷↓ࢆㄪ࡭ࡿࡓࡵ࡟ࠊㄪ〇ࡋࡓゐ፹ࡢ Rh K ẇXAFS

ᐃࢆ SAGA-LS BL07 ࡟࠾࠸࡚⾜ࡗࡓࠋEXAFS ࢫ࣌ࢡࢺࣝࡢᙧ≧ࡣࠊ࢔࣑ࣥࡢ᭷↓࣭ᅛᐃ໬㔞࡟౫Ꮡࡏࡎࠊ୍ᐃ࡛࠶ࡗࡓ (Fig. 1)ࠋࡇࡢ⤖ᯝࡼࡾࠊྠ୍⾲㠃ࡢ࢔࣑ࣀᇶࡣ┤᥋ Rh㘒య࡜┦஫స⏝ࡍࡿࡢ࡛ࡣ࡞ࡃࠊRh 㘒య࡜࡜ࡶ࡟ᇶ㉁ศᏊ࡬༠ዌⓗ࡟స⏝ࡋ࡚࠸ࡿ࡜࠸࠼ࡿࠋ
⥆࠸࡚ࠊPd 㘒య࡜᭷ᶵᐁ⬟ᇶࢆྠ୍ࢩࣜ࢝⾲㠃࡟ᅛᐃࡋࡓゐ፹ࢆ㛤Ⓨࡋࡓࠋ᭷ᶵᐁ⬟ᇶ࡜ࡋ࡚᭷ᶵᙉሷᇶ DABCO ࢆ⏝࠸ࡿ࡜ࠊPd 㘒యࡢάᛶࡀ኱ᖜ࡟ྥୖࡋࠊࢣࢺ࢚ࢫࢸࣝࡢ࢔ࣜࣝ໬཯ᛂ࡟࠾ࡅࡿゐ፹ᅇ㌿ᩘ (TON) ࡀ 100000 ࢆ㉸࠼ࡓ[2]ࠋࡇࡢ್ࡣࠊ᪤ሗࡢ Pd ゐ፹⣔࡜ẚ㍑ࡋ࡚
᭱ࡶ㧗࠸್࡛࠶ࡿࠋᅛᐃ໬ Pd 㘒యࡢᒁᡤᵓ㐀ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊSAGA-LS BL07 ࡟࠾࠸࡚Pd K ẇ XAFSᐃࢆᐇ᪋ࡋࡓࠋEXAFS ࢫ࣌ࢡࢺࣝࡢ Pd-P/Cl ẇࡢ CF ゎᯒ࠿ࡽࠊPd 㘒యࡣᵓ㐀ࢆಖࡗࡓࡲࡲࢩࣜ࢝⾲㠃࡟ᅛᐃࡉࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ୍᪉࡛ࠊDABCO ➼ࢧ࢖ࢬࡢ኱
ࡁ࡞ᐁ⬟ᇶࢆඹᏑࡉࡏࡿ࡜ࠊPd 㘒యࡢࡳࡢሙྜ࡜ẚ㍑ࡋ࡚ࠊCF ゎᯒ᫬ࡢ DW ᅉᏊࡀቑຍࡋࡓ(Fig. 2)ࠋPd-P/Cl ⤖ྜ㊥㞳ࡣ᭷ᶵᐁ⬟ᇶࡢᏑᅾ࡟࡯࡜ࢇ࡝ᙳ㡪ࢆཷࡅ࡞࠸ࡓࡵࠊDW ᅉᏊࡢቑຍࡣ ıstatic ࡢቑຍࠊࡍ࡞ࢃࡕ᭷ᶵ⬟ᇶ࡜ࡢ❧యⓗ┦஫స⏝࡟ࡼࡿ Pd 㘒య㦵᱁ࡢṍࡳ࡟㉳ᅉࡍࡿࠋࡇࡢ⤖ᯝࡣࠊPd 㘒య࡜᭷ᶵᐁ⬟ᇶࡀࢩࣜ࢝⾲㠃࡛㏆᥋ࡋ࡚Ꮡᅾࡍࡿࡇ࡜ࢆ♧ࡋ࡚࠾ࡾࠊ㏆᥋ࡋ
ࡓゐ፹άᛶⅬࡀ༠ዌⓗ࡟ᇶ㉁ศᏊࢆάᛶ໬ࡍࡿ༠ྠゐ፹స⏝ࡢᏑᅾࢆᨭᣢࡋ࡚࠸ࡿࠋClPdII PhP PhPh PPhNO
SiFig. 1 EXAFS spectra of SiO2-supported Rh complex with (blackand red solid lines) and without tertiary amine (black dashed)

NClcatalyst¨ı2/ Å2㽢10–3

NCl
PdII PhP PhPh P
PhN

Si OEtOSiMeO
Si OO
SiSiOSi

Si OEtOSi

SiO2/PP Pd

SiO2/DABCO/PP Pd

2.80㼼0.20

5.05㼼0.20

Fig. 2 Structure of SiO2-supported Pd complexes
and Debye-Waller (DW) factor values[1] H. Noda, K. Motokura, W.-J. Chun et al. Catal. Sci.Technol. 2015, 5, 2714.
[2] K. Motokura, K. Saitoh, H. Noda, W.-J. Chun et al. ChemCatChem 2016, 8, 1386; Catal. Sci.
Technol. 2016, in press (DOI: 10.1039/C6CY00593D).

ਸ਼৚ృପ३থॡটॺটথ୾ଢ଼஢७থॱ‫ش‬ଢ଼஢ਛટਾઔভ‫؜‬१থওॵ७೭ၓಕ৬਀એदभੈ৊ඡᄘ੿৷ੈས஍ટपेॊખૢയਤಕ৒৲჻৬ඡᄘभ;$)6पेॊ
ଡୗੰෲधੈ৊ඡᄘ੿৷भੰ৥ূ਎ੵ঵প৾Ń੟ସ৶ੵ৾੹Ńૢ৷৲৾௺Ń॔঑ঀ੦૓ਟभව੦ਡध෷ਡधभੈ৊ඡᄘ੿৷
Y. Kubota et al. Chem. Lett. (2003); V. S.-Y. Lin et al. Angew. Chem. Int. Ed. (2005)
A. Katz et al. J. Am. Chem. Soc. (2006); M. E. Davis et al. Angew. Chem. Int. Ed.
(2006); H. Kung et al. Top. Catal. (2008) [review] ; C. W. Jones et al. J. Am. Chem.
Soc. (2012); K. Motokura et al. J. Am. Chem. Soc. (2007), etc…

মಠ ௏সര჻৬धથਃව੦भಕ৬਀એदभੈ৊ඡᄘ੿৷Aৼખघॊણਙਡभુோ‫؟୻ق‬෷‫؞‬ව੦‫ك‬

3G჻৬'$%&2ಕ৒৲ඡᄘभ৹ଲBBA(Substrate)(Product)

1. SiO2/DABCO/PP-Pd

2. SiO2/diamine/Rh/NEt2

余&105

▏ٕ7URVWખૢ余Ph*

*余(e)

余*

余*

余余(d)

Catalyst

Conv.
of 1 [%]

Yield of3 [%]Yield of4 [%]TON

SiO2/PP-Pd

98

4049230

SiO2/Me/PP-Pd

83

62

21170

SiO2/Hexyl/PP-Pd

90

55

31200

**余*䕿୺䛺Ⅳ⣲㦵᱁䛾⥔ᣢ䜢☜ㄆ
*䕿Pd㘒యᵓ㐀䛾ヲ⣽䛿୙᫂

EtO

EtO

*ecd(c)*ba(b)CHCl3

SiO2/DABCO/PP-Pd>99

1881300
PhEtO

ऩछųƇ჻৬भણਙऋ਱঱खञभऊ‫ء‬Ńe cf‫ڀ‬Ń ŧŤťŦŲपेढथųƇ჻৬ଡୗम୶஭॑ਭऐथःॊभऊ‫ءء‬Ń200150

10013d50

C Chemical Shift / ppmEtOba(a)03G.ᅊ(;$)6५ঌॡॺঝ

(;$)6५ঌॡॺঝभ&)ੰෲ

5

Catalyst (Shell: Pd-P/Cl)

43

SiO2/PP-Pd

2

SiO2/Me/PP-Pd

k3 / k1

0

SiO2/Hexyl/PP-Pd-1

SiO2/DABCO/PP-Pd-2

Nr (Å)

2.6

2.26

∆σ2
∆E (eV)(Å210–3)
2.80
–2.07

s0.4

s0.01

s0.20

s2.03

2.6

2.27

3.63

–6.81

s0.4

s0.01

s0.20

s2.09

2.9

2.27

4.86

–3.11

s0.4

s0.01

s0.20

s2.00

3.0

2.26

5.05

–0.61

s0.5

s0.01

s0.20

s1.98

Rfactor
(%)
1.95
1.23
2.87
3.05

σ2 = σdynamic2 + σstatic2-3

ͽVWDWLFभ૗৲ ‫ ڀ‬થਃী৕धभয়৬௽૩पेॊ჻৬෗તभኾा॑ંྮ

-4-502468

1012'$%&2ध3G჻৬
म੺மखथோ૔खथ
ःॊ‫آ‬k / Å-1ಕ৒৲৐৏‫ؚ‬DABCOभથ૮पঢ়ॎैङ‫ؚ‬५ঌॡॺঝभਜ਼ৼऋऺऻ౥৸प঳ಱ‫ڀ‬჻৬भ੦মଡୗम೐੅औोथःॊ ChemCatChem 2016, 8, 331୳৒ખૢਃଡ

SiO2 surface<<਼ੀਈৈभඡᄘ৚ૡਯ 721 ॑୸ਛ

CF analysis of EXAFS
Shell: Pd䠉P/Cl
FDWDO\VW Ŧű
EHIRUH 3.0 㼼0.5

DIWHU

2.3 㼼0.4(Pd: 0.21 μmol)‫پ‬ऒोऽदभਾઔऔोथःॊ3Gඡᄘ ੷றදभ+ਬऌ௷ऌ॑ൣअ௺‫ك‬ 721‫ع‬Catal. Sci. Technol. 2016, 6, 5380

সര჻৬धથਃව੦भಕ৬਀એदभੈ৊ඡᄘ੿৷
AA5K჻৬௻॔঑থಕ৒৲ඡᄘभ৹ଲ

BB(Substrate)

1. SiO2/DABCO/PP-Pd(Product)

2. SiO2/diamine/Rh/NEt2&KDUDFWHUL]HGE\VROLGVWDWH105;$)6;36HOHPHQWDODQDO\VLVইख़ॽঝ঍क़෷भહਸખૢ5K.ᅊ;$1(6५ঌॡॺঝ6L2GLDPLQH5K1(W
6L2GLDPLQH5K ‫ڀ‬ુप੼भ5K჻৬धథ๚

SiO2/diamine/
Rh/NEt2(recover)&DWDO\VW&RQYRI(QRQH  <LHOG  

SiO2/diamine/Rh/NEt2

2828

SiO2/diamine/Rh

1010

SiO2/diamine/Rh+
dietylbutylamine

0808

SiO2/diamine/Rh+
SiO2/NEt21010

SiO2/diamine/Rh
SiO2/diamine/Rh/NEt2৹ଲखञඡᄘরभ
5Kரम੼

[RhI(cod)OH]2

RhIII2O3
Rh0 foilऩछŵƋ჻৬भણਙऋ਱঱खञभऊ‫ء‬Ń‫ڀ‬Ń Ŗ௻॔঑থपेढथŵƋ჻৬ଡୗम୶஭॑ਭऐथःॊभऊ‫ء‬Ń

5K.ᅊ(;$)6५ঌॡॺঝ

SiO2/diamine/Rh/NEt2)7RIƎZHLJKWHG5K.ᅊ(;$)6५ঌॡॺঝ
Curve-Fitting analysis
SiO2/diamine/Rh

䞉Rh: 0.412 mmol/g,䞉amine: 0.44 mmol/g

SiO2/diamine/Rh/NEt2Sample

Nr (Å)σ2 (Å2 ΔE0× 10–3) (eV)Rf(%)

SiO2/diamine/ 6.8
Rh/NEt2
± 1.5

2.10
5.44
± 0.02 ± 1.75

-8.46
0.022
± 3.81

SiO2/diamine/ 6.8
Rh
± 1.5

2.09
5.35
± 0.02 ± 1.68

-10.2
± 4.06

0.022

Fitting range: 1.2–2.0 (Å) (R-space)

Rh–C/O[RhI(cod)OH]2

䞉Rh: 0.054 mmol/g
䞉amine: 0.07 mmol/g

Rh–O–Rh
Rh–O

RhIII2O3
Rh–Rh

ಕ৒৲୤‫ؚ‬3௻॔঑থभથ૮पঢ়ॎैङ‫ؚ‬५ঌॡॺঝऋऺऻ঳ಱ

Rh0 foil䞉Rh: 0.528 mmol/g

SiO2/diamine/Rh/NEt2&)ੰෲभ੥ટम‫୳ؚ‬৒5K჻৬ଡୗ੍॑੅

‫ڀ‬჻৬भ੦মଡୗमःङोु৊঳୳৒ખૢਃଡ

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K\GURO\VLV

DPLQHFRRUGLQDWLRQABWUDQVPHWDODWLRQK. Motokura et al.,ChemCatChem 2016, 8, 331.
Catal. Sci. Technol. 2016, 6, 5380.
Catal. Sci. Technol. 2015, 5, 2714.
'RXEOH$FWLYDWLRQ&DWDO\VLV
Catal. Sci. Technol. 2015, 5, 2714

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