2009A1848                          BL14B2

㕲ゐ፹ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂ࡟࠾ࡅࡿゐ፹άᛶ✀ࡢゎᯒ
Analysis on Catalytic Active Species for Iron- Catalyzed Cross-Coupling␊ᒣ ⌶ḟ a, 㧗㇂ ග a, Ụཱྀஂ㞝 b, ୰ᮧ ṇ἞ a
Takuji Hatakeyamaa, Hikaru Takayaa, Hisao Eguchib, Masaharu Nakamuraaaி㒔኱Ꮫ໬Ꮫ◊✲ᡤ, b ᮾࢯ࣮࣭ࣇ࢓࢖ࣥࢣ࣒ᰴᘧ఍♫ Institute for Chemical Research, Kyoto University, bTOSOH FINECHEM. CO.
a㕲࢔ࢭࢳࣝ࢔ࢭࢺࢼ࣮ࢺ㻔II/III㻕—ࢪ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚ㻔Xantphos㻕࠾ࡼࡧሷ໬㕲㻔II/III㻕–ࢪ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚ㻔TMS-SciOPP㻕ࡢࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂ⏝ゐ፹࡟㛵ࡋ㸪཯ᛂ⣔ࡢ⁐ᾮ XAFS ᐃࢆ⾜ࡗࡓ㸬Fe k-edge XANES ࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡ࢚ࢵࢪ㻔1d̽4p 㑄⛣㻕ࡼࡾ㸪ゐ፹άᛶ✀㻔A㻕ࡣ㸪͆–2 ౯͇ࡢ࢔ࢽ࢜ࣥᛶࡢ Fe άᛶ✀㸪ゐ፹άᛶ✀㻔A㻕ࡣ㸪͆㸩2 ౯͇ࡢ Fe άᛶ✀ࡀ⏕ᡂࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸬1s–3dࣉ࢚ࣜࢵࢪ࡟୍ᐃᙉᗘࡢ྾཰ࡀ࠶ࡾ㸪࡝ࡕࡽࡶ㕲୰ᚰࡢ㓄఩⎔ቃ࡟㛵ࡋ࡚ࢸࢺࣛ࡬ࢻࣛࣝ 㻔Td㻕㻌 ᵓ㐀ࡢゐ፹άᛶ✀ࡀ⏕ᡂࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸬ࡇࢀࡣపཎᏊ౯≧ែ㻔0 ౯㻕ࢆάᛶ✀࡜ࡍࡿࢽࢵࢣ
ࣝࡸࣃࣛࢪ࣒࢘ゐ፹࡜ࡣ኱ࡁࡃ␗࡞ࡾ㸪㕲ゐ፹ࡢ≉␗࡞཯ᛂᛶࢆ⢭ᐦไᚚࡍࡿ᪉ἲࢆ㛤Ⓨࡍࡿୖ࡛㸪㔜せ࡞ᣦ㔪࡜࡞ࡿⓎぢ࡛࠶ࡿ㸬࣮࣮࢟࣡ࢻ㸸 㕲᪘㔠ᒓゐ፹ࠊࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࠊXANES⫼ᬒ࡜◊✲┠ⓗ㸸ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࡣᾮᬗ㸪᭷ᶵ EL㸪་⸆࣭㎰⸆ྜᡂ➼ࡢ᭷⏝໬Ꮫ≀㉁⏕⏘ࡢࡓࡵࡢᇶ┙ᢏ⾡࡛࠶ࡿ㸬⌧ᅾ㸪ᕤᴗゐ፹࡜ࡋ࡚ࣃࣛࢪ࣒࢘㻔Pd㻕ࡸࢽࢵࢣࣝ㻔Ni㻕࡞࡝ࡢᕼᑡ㔠ᒓඖ⣲㻔ࣞ࢔࣓ࢱࣝ㻕ࡀ⏝࠸ࡽࢀ࡚࠸ࡿࡀ㸪ࡇࢀࡽࡣ㝈ࡽࢀࡓ㈨※࡛࠶ࡿࡔࡅ࡛࡞ࡃ㸪ᆅᇦ೫ᅾᛶࡀ㧗࠸ࡓࡵ㸪ᑗ᮶ⓗ࡞Ᏻᐃ౪⤥ࡢ⥔ᣢࡀᠱᛕࡉࢀ࡚࠸ࡿ㸬ࡇࡢࡼ࠺࡞⫼ᬒࡢୗ㸪ᡃࠎᆅẆᏑᅾ㔞ࡢ኱ࡁ࡞㕲ゐ፹ࢆ⏝࠸㸪ࡇࢀࡽࡢᕼᑡ㔠ᒓゐ፹ࢆ௦᭰ࡋ㸪ࡉࡽ࡟ࡣࡇࢀࡽࢆ෽㥙ࡍࡿゐ፹ࡢ㛤Ⓨࢆ⾜࠸㸪ሷ໬㕲–ࢪ࢔࣑ࣥ㓄఩Ꮚ㻔TMEDA㻕[1]㸪ሷ໬㕲–ࢪ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚ㻔TMS-SciOPP㻕[2]㸪ࣇࢵ໬㕲—࢝ࣝ࣋ࣥ㓄఩Ꮚ㻔SIPr㻕 [3]㸪㕲࢔ࢭࢳࣝ࢔ࢭࢺࢼ࣮ࢺ—ࢪ࣍ࢫࣇ࢕ࣥ㓄఩Ꮚ㻔Xantphos㻕࡞࡝ࡢ᪂つ㕲ゐ፹⣔ࢆぢฟࡋ࡚ࡁࡓ㸬ᮏゐ፹⣔ࡣ㸪ᚑ᮶ࡢ Pd㸪Ni ゐ፹ࡼࡾࡶ㧗άᛶ࡛࠶ࡾ㸪ࡇࢀࡲ࡛฼⏝ࡀ㐜ࢀ࡚᮶ࡓ୙άᛶ࡞ሷ໬࢔ࣝ࢟ࣝࡸሷ໬࢔࣮ࣜࣝࢆ཯ᛂᇶ㉁࡜ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࡇ࡜࠿ࡽ㸪ࢳࢵࢯ࠾ࡼࡧᮾࢯ࣮࠿ࡽ≉チฟ㢪ࡉࢀ㸪ᚋ⪅࡛ࡣࣃ࢖ࣟࢵࢺࣉࣛࣥࢺࡀ✌ാࡋ࡚࠸ࡿ㸬ࡑࡇ࡛௒ᅇࡢ ᐃ࡛ࡣ㸪኱つᶍ࡞⏕⏘ィ⏬࡟ྥࡅࡓ᭦࡞ࡿ཯ᛂຠ⋡ࡢྥୖࢆ┠ᣦࡋ㸪in situ XAFS ᐃ࡟ࡼࡿ Fe ゐ፹άᛶ✀㻔A㸪B㻕ࡢྠᐃࢆ⾜ࡗࡓ㻔ᅗ 1㻕䠊㻌ᅗ 1㸬ࣁࣟࢤࣥ໬࢔ࣝ࢟ࣝ㸭࢔࣮ࣜࣝࢆồ㟁Ꮚ๣࡜ࡍࡿ㕲ゐ፹ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 ࢸࣇࣟࣥ❆௜ࢭࣝࢆ⏝࠸㸪ྛ✀཯ᛂ⁐ᾮࡢ XAFS ᐃࢆ⾜ࡗࡓ㸬Fe ゐ፹άᛶ✀ A ࡟㛵ࡋ࡚ࡣ㸪ゐ፹๓㥑య࡜ࡋ࡚ Fe㻔acac㻕2㻔A㻕࡜ Fe㻔acac㻕3㻔A’㻕ࡢ␗࡞ࡿ౯ᩘࡢࡶࡢࢆ⏝࠸᳨࡚ウࡋࡓ㸬ᚓࡽࢀࡓ
XANES ࢫ࣌ࢡࢺࣝࢆᶆ‽ヨᩱࢹ࣮ࢱ࡜ඹ࡟ᅗ 2 ࡟♧ࡋࡓ㸬ఱࢀࡢ཯ᛂ⁐ᾮࡢ XANES ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࡶ㸪ࣆ࣮ࢡ࢚ࢵࢪ㻔1d̽4p 㑄⛣㻕ࡀ 7080eV ࡜࠸࠺ప࢚ࢿࣝࢠ࣮࡟࠶ࡾ㸪๓㥑యࡢ౯ᩘ࡟ࡼ
ࡽࡎ͆–2 ౯͇ࡢ࢔ࢽ࢜ࣥᛶࡢ Fe άᛶ✀ࡀ⏕ᡂࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸬ࡇࢀࡣ Pd ࡸࢽࢵࢣࣝNi ゐ፹࡛ࡣぢࡽࢀ࡞࠸⌧㇟࡛࠶ࡾ㸪㕲ゐ፹ࡢ≉␗࡞ゐ፹άᛶࡢཎᅉ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬ᅗ 2㸬ゐ፹άᛶ✀ A ࠾ࡼࡧ A’ࡢ XANES ࢫ࣌ࢡࢺࣝ

 Fe ゐ፹άᛶ✀ B ࡟㛵ࡋ࡚ࡶྠᵝ࡟㸪ゐ፹๓㥑య࡜ࡋ࡚ FeCl2 ࡜ FeCl3 ࡢ␗࡞ࡿ౯ᩘࡢࡶࡢࢆ⏝࠸᳨࡚ウࡋࡓ㸬ᚓࡽࢀࡓ XANES ࢫ࣌ࢡࢺࣝࢆᶆ‽ヨᩱࢹ࣮ࢱ࡜ඹ࡟ᅗ 3 ࡟♧ࡋࡓ㸬ఱࢀࡢ཯ᛂ
⁐ᾮࡢ XANES ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࡶ㸪ࣆ࣮ࢡ࢚ࢵࢪ㻔1d̽4p 㑄⛣㻕ࡀ 7118eV ࡟࠶ࡾ㸪๓㥑యࡢ౯ᩘ࡟ࡼࡽࡎ͆㸩2 ౯͇ࡢ Fe άᛶ✀ࡀ⏕ᡂࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸬ࡲࡓ㸪7115eV ࡟ࣉ࢚ࣜࢵࢪࣆ࣮ࢡ㻔1d̽3d 㑄⛣㻕ࢆ☜ㄆࡋ࡚࠾ࡾ㸪άᛶ✀ࡣࢸࢺࣛ࡬ࢻࣛࣝᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ㸬
EXAFS ࢫ࣌ࢡࢺࣝ࠿ࡽࡣ㸪⣙ 2.3ύࡢ఩⨨࡟㸲ࡘࡢཎᏊ㻔P or C or Br㻕ࢆ᭷ࡋࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡾ㸪άᛶ✀ B ࡣ Ar2Fe·TMSSciOPP ࡛࠶ࡿ࡜᥎ᐃࡉࢀࡿ㸬
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ᅗ 3㸬ゐ፹άᛶ✀ B ࠾ࡼࡧ B’ࡢ XANES ࢫ࣌ࢡࢺࣝ௒ᚋࡢㄢ㢟㸸 ௨ୖࡢࡼ࠺࡟⏝࠸ࡿ࣍࢘⣲໬ྜ≀࡟ࡼࡾ㕲ゐ፹άᛶ✀ࡢ౯ᩘࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ㸬௒ᚋ㸪ࡇࡇ࡛ᚓࡽࢀࡓ▱ぢࢆඖ࡟㸪㧗άᛶ᭷ᶵ㕲㘒యࡢྜᡂ࡜ࡑࢀࢆ⏝࠸ࡓᶵ⬟ᛶ᭷ᶵᮦᩱࡢ኱つᶍ࡞⏕⏘ࣉࣛࣥࢺࡢ❧ࡕୖࡆ࡟╔ᡭࡍࡿ㸬ྠ᫬࡟㸪⌮ㄽ໬Ꮫⓗゎᯒ࡜ẚ㍑ࡍࡿࡇ࡜࡛ࡇࢀࡲ࡛඲ࡃ᫂ࡽ࠿࡜࡞ࡗ࡚࠸࡞࠸㕲ゐ፹ࢡࣟࢫ࢝ࢵࣉࣜࣥࢢ཯ᛂࡢ཯ᛂᶵᵓࢆ᫂ࡽ࠿࡜ࡋ࡚࠸ࡃணᐃ࡛࠶ࡿ㸬ཧ⪃ᩥ⊩㸸
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