1P12 ࢲ࢛ࢨࣤ㓗࢛ࣤ㍂㒼నࡊࡒ࢜ࣜ࣍ࣤ㓗ᯣᶣࣜࢷࢼ࣑(II,III) ᰶ㘊మ࡞ࡗ࠷࡙DFTゝ⟤࡞ᇱࡘࡂ㞹Ꮔ≟ឺࡡ⩻ᐳ ې༖⏛┷ 㸡ᓧᒜ༡ྍ 㸡ᚒདḿ༡ 㸡ờ୕ᓤ ᓞ᰷ኬᏕኬᏕ㝌⥪ྙ⌦ᕝᏕ◂✪⛁ࠚ ᮿỜᕰこᕖ⏣ ᒜᙟኬᏕ⌦Ꮥ㒂∸㈻⏍Ꮥ⛁ࠚ ᒜᙟᕰᑚⓉᕖ⏣ 㛭こᏕ㝌ኬᏕ⌦ᕝᏕ㒂Ꮥ⛁ࠚඹᗔ┬⏛ᕰᏕᅧ ୍┘ ␊ᆀ ࠘⥬ゕ࠙㸩ࡡ࢜ࣜ࣍ࣤ㓗࢛ࣤ㸧ࡡ㔘ᒌ࢛ࣤ 㸝Mn+㸞ࢅฦᏄහᯣᶣࡊࡒࣚࣤࢰࣤᆵᰶ㘊మࡢࠉ㔘 ᒌ࢛ࣤ㛣ࡡᙁ࠷┞பష⏕࡞ᇱࡘࡀ M-M ⤎ྙ⏍ࡋ ࡾࠊ౮㞹Ꮔࡢࠉ┞பష⏕࡚⏍ࡋࡒȪࠉȧ࠽ࡻࡦț㌮㐠 ࡞Ꮛᅹࡌࡾࠉኣࡂࡡሔྙࠉཬ☚ᛮࡡ㞹Ꮔ㒼⨠࡛ࡾࠊ ࡊ࠾ࡊࠉࣜࢷࢼ࣑(II,III)㘊మࡡሔྙࡢࠉᅒ㸦࡞♟ࡌ ࡻ࠹࡞ȧ*࡛ț*㌮㐠ഃ↓࡞⦨㔔ࡊ࡙࠷ࡾࡒࡴ㸨ࡡ ᑊ㞹Ꮔࢅ᭯ࡌࡾᖏ☚ᛮࡡ㞹Ꮔ㒼⨠࡛ࡖ࡙࠷ࡾࡆ࡛ ࠾ࡼࠉ☚ẴⓏ࡞⮾ᣚࡒࡿࡾ∸㈻࡚࠵ࡾ 1)ࠊᮇ◂✪ II,III + ࡚ࡢࠉࣅࣁࣜ㓗࢛ࣤ㸝piv 㸞ࢅฦᏄහᯣᶣ㒼నᏄ࡛ࡊࠉ ᅒ㸦 (Ru2 ) ࡡ㞹Ꮔ㒼⨠ ࢲ ࢛ ࢨ ࣤ 㓗 ࢛ ࣤ (NCS ) ㍂ 㒼 న ࡊ ࡒ (NBu4)][Ru2(piv)4(NCS)2]ࢅྙᠺࡊࠉࡐࡡ⤎ᬏᵋ㏸ࢅỬᏽࡌࡾ࡛࡛ࡵ࡞ࠉᰶහࡡᑊ 㞹Ꮔࡡ㒼నᏄࡡ㟸ᑻᅹ࡞ࡗ࠷࡙ࠉNMR ࢪ࣋ࢠࢹࣜ࡞࠽ࡄࡾ㒼నᏄࡡᖏ☚ᛮࢨࣆ ࢹ࠽ࡻࡦ DFT ゝ⟤⤎ᯕ࡞ࡗ࠷࡙ࡡ⩻ᐳ࠾ࡼ᳠ゞࡊࡒࡡ࡚ሒ࿈ࡌࡾࠊ ࠘⤎ᯕ࠙ᅒ㸧࡞[Ru(piv)4(NCS)2]-ࡡᵋ㏸ࢅ♟ࡌࠊ Ru-Ru ࠉR-N (NCS-) ⤎ྙ㊝ 㞫ࡢ ࠉࡐࡿࡑ ࡿࠉ 2.2947(5) Å ࠽ࡻࡦ 2.24(2) Å ࡚࠵ࡖࡒࠊ13C NMR ࢪ࣋ࢠࢹࣜ࡞࠽࠷࡙㸝CD2Cl2 ୯ࠉ298 K㸞ࠉࣅࣁ ࣜ㓗࢛ࣤࡡ࢜ࣜ࣍ࢼࣜ⅛⣪ࡢ-729 ppm ࡞ࠉࢲ ࢛ࢨࣤ㓗࢛ࣤࡡ⅛⣪ࡢ 376 ppm ࡞ふῼࡈ ࡿࠉࣜࢷࢼ࣑(II,III)ᰶ࠾ࡼ㒼నᏄࡡᑊ 㞹Ꮔࡡ㟸ᑻᅹࢅ☔ヾࡊࡒࠊᑊ㞹Ꮔࡡ㒼నᏄ ࡡ㟸ᑻᅹࡢࠉDFT ゝ⟤⤎ᯕ࡚ㄕ᪺࡚ࡀࡾࡻ ࠹࡚࠵ࡾࠉᖏ☚ᛮࢨࣆࢹ࡛ࢪࣅࣤᐠᗐࡡレ⣵ 㛭౿࡞ࡗ࠷࡙ࡢ⌟ᅹ᳠ゞ୯࡚࠵ࡾࠊ 1) Mikuriya, D. Yoshioka, and M. Handa, Coord. Chem. Rev., 2006, 250, 2194.Ở ᅒ㸧 [Ru2(piv)4(NCS)2]-ࡡᵋ㏸
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