2P042䝭䝷䝃䝏䝍ୌ౮䜨䜮䝷䛱䜎䜑໩Ꮥ⤎ྙว᩷㐛⛤䛱㛭䛟䜑⌦ㄵⓏ◂✪㻃 㻃ࠤ ┞ᑊㄵⓏ䝦䝋䝯හṾ䝡䝊䝷䜻䝧䝯䟺MCP䟻Ἢ䛱䜎䜑ཬᚺよᯊ ࠤ(ஐኬ㝌⥪⌦ᕝ1㸡CREST2)䕵᲻ ᐰᨼ1䟾ሪᮇ ᫬ஒ1䟾୔ይỄష1,2i.ᗆ࣬┘Ⓩ ࣚࣤࢰࢼࢺୌ౮࢕࢛ࣤࡢ᭯ᶭฦᏄ࡛Ẵ┞࡚ཬᚺࡊ㸡㸝௥᭨㸞ࣆࣞࣤฦᏄࡡ C-F ⤎ྙࢅり፳Ⓩ࡞ว᩷ࡌࡾࡆ࡛࠿▩ࡼࡿ㸡⎌ሾᕝᏕⓏ࡝ふⅤ࠾ࡼἸ┘ࡈࡿ࡙࠷ࡾ㸣ࡱࡒ㸡ཬᚺ RF + Ln+ Ѝ LnF+ + R (Ln= La-Lu; R= CH3, C6H5) ࡡຝ⋙ࡢ㸡ࣚࣤࢰࢼࢺ࢕࢛ࣤ࡞౪Ꮛࡊ࡙࿔᭿Ⓩ࡞ን໩ࡌࡾࡆ࡛࠿▩ࡼࡿ㸡⌦ᏕⓏふⅤ࠾ࡼࡵ㸡ࡐࡡཬᚺᶭᵋࡡよ᪺ࡢ⮾࿝῕࠷㸣ࡆࡡ C-F ⤎ྙว᩷ཬᚺ࡞ࡢ㸡ࡆࡿࡱ࡚࡞㸡ᅒ 1 ࡞♟ࡌ (a) ᣼ථѸ ⬲㞫ᶭᵋ㸡ཀྵࡦ (b) ࡵࡽᡬࡔᶭᵋࡡ஦ࡗࡡཬᚺᶭᵋ࠿㸡Cornel࣬Hertwigh࣬Zhang࣬Koyanagi ࡼ࡞ࡻࡽᥞ᱄ࡈࡿ࡙࠷ࡾ㸣ࡓ࠿㸡ᮅࡓࡐࡡཬᚺᶭᵋࡢỬᏽࡈࡿ࡙࠷࡝࠷ [1-4]㸣ᮇ◂✪࡚ࡢ㸡᭩㎾ᠻࠍ࠿ GAMESS [5]୕࡚Ᏸᠺࡊࡒ┞ᑊㄵⓏ࣓ࢸࣜහṾ࣎ࢷࣤࢨࣔࣜ㸝MCP㸞࡞ࡻࡾฦᏄᵋ㏸᭩㐲໩ࣈࣞࢡ࣑ࣚࢅ ab initio ฦᏄ㌮㐠Ἢ࡛㏻ິࡊ㸡ࣚࣤࢰࢼࢺୌ౮࢕࢛ࣤࡡཬᚺᛮ࡛㞹Ꮔᵋ㏸ࡡ㛭౿ࢅ⌦ㄵⓏふⅤ࠾ࡼ᥀ࡖࡒࡡ࡚ሒ࿈ࡌࡾ㸣(a)
FR

Ln+ + R-F

LnF+ + R
Lninsertione- harpoon(b)
Ln+ + R-F

ᅒ1elimination

Ln+Ln2+-F-F-R

R

LnF+ + Rࣚࣤࢰࢼࢺୌ౮࢕࢛ࣤ࡞ࡻࡾ C-F ⤎ྙว᩷ཬᚺᶭᵋ㸰(a) ᣼ථѸ ⬲㞫ᶭᵋ㸡(b) ࡵࡽᡬࡔᶭᵋiゝ⟤᪁Ἢ ࣚࣤࢰࢼࢺࢅྱࢆࡓ ab initio ฦᏄ㌮㐠ゝ⟤࡚ࡢ㸡ゝ⟤ㇿⲬࢅ΅ࡼࡌࡒࡴ㸡ୌ⯙࡞㸡᭯ຝහṾ࣎ࢷࣤࢨࣔࣜ㸝ECP㸞࠿౐ࢂࡿࡾ㸣ࡓ࠿㸡ECP Ἢ࡚ࡢ㸡౮㞹Ꮔ㌮㐠ࡡ⟿ᵋ㏸ࢅḿࡊࡂ්⌟࡚ࡀࡍ㞹Ꮔ┞㛭࠿㐛ኬフ౮ࡈࡿࡾࡒࡴ㸡⢥ᐠ࡝ฦᏄ∸ᛮೋࡡぜ✒ࡵࡽ࡞୘Ꮽ࠿ṟࡾ㸣ࡐࡆ࡚ᮇ◂✪࡚ࡢ㸡౮㞹Ꮔ㌮㐠ࡡḿࡊ࠷⟿ᵋ㏸ࢅ්⌟ࡊ㸡ࡻࡽ⢥ᐠ࡞ฦᏄ∸ᛮೋࢅゝ⟤࡚ࡀࡾ࣓ࢸࣜහṾ࣎ࢷࣤࢨࣔࣜ㸝2(5㸞Ἢࢅ㐲⏕ࡊ㸡㞹Ꮔ┞㛭࣬┞ᑊㄵຝᯕࢅྜྷ᫤࡞ཱིࡽ᡽ࡖࡒ ab initio ゝ⟤㸝MP2࣬CAS(RAS) SCF࣬CASPT2㸞࡞ࡻࡾᵋ㏸᭩
㐲໩࢙࣬ࢾ࣭ࣜ࢟ゝ⟤ࢅᐁ⾔ࡊࡒ㸣௑ᅂࡢ㸡Ce࣬Gd࣬Yb ࡡሔྙࡡཬᚺ⤊㊪よᯊࢅ⾔ࡖࡒ㸣ゝ⟤࡞౐⏕ࡊࡒᇱᗇ㛭ᩐࡢ㸡௧ୖ࡞♟ࡊࡒ㏳ࡽ࡚࠵ࡽ㸡㞹Ꮔ┞㛭⏕ฦᴗᇱᗇ⣌ࢅ௛㝮ࡊ࡙࠷ࡾ㸣㸝ࢪࣅࣤ㌮㐠Ѹ ┞பష⏕ࢅ㝎ࡂ㸞┞ᑊㄵຝᯕࡢ㸡┞ᑊㄵⓏ MCP ࢅ౐⏕ࡌࡾࡆ࡛࡞ࡻࡽ⩻៎ࡊࡒ㸣Ce࣬Gd࣬Yb : MCP-tzp [10s 10p 9d 10f 3g]/(4s 4p 3d 3f 1g) [6]㸡 C࣬F࣬H : cc-pVTZ
CAS(RAS) SCF ゝ⟤࡚⏕࠷ࡾὩᛮ✭㛣࡞ࡢ㸡ḗࡡ㌮㐠ࢅ㐽ᢝࡊࡒ㸣
Ln : 4f࣬6s࣬(5d) ㌮㐠 (Ln = Ce, Gd, Yb)㸡 F: 2p ㌮㐠

Energy / kcal mol-1

MP2 ゝ⟤࡞ࡢ GAMESS [5] ࢅ㸡CAS(RAS) SCF㸡CASPT2 ゝ⟤࡞ࡢ MOLCAS [7] ࢅ౐⏕ࡊࡒ㸣Reactant
TS0.0

Product-5.7-10.49-22.63IM1(intermediate)-26.25IM2(intermediate)

Reaction coordinate
ᅒ 2 C-F ⤎ྙว᩷ཬᚺ CH3F + Ln Ѝ LnF+ + CH3 ࡡཬᚺ⤊㊪ᶅᘟᅒ㸝྘≟ឺࡡᵋ㏸ࡢᅒ 2 ཤ↯㸞+i⤎ᯕ࡛⩻ᐳ ཬᚺ⤊㊪ࡡよᯊࢅጙࡴࡾ๑ṹ㝭࡛ࡊ࡙㸡ࡱࡍ㸡┞ᑊㄵⓏ MCP Ἢࡡ⢥ᗐࢅ LnF (Ln =Ce, Gd, Yb) ࡡฦකᏕᏽᩐࢅぜ✒ࡵࡾࡆ࡛࡞ࡻࡽࢲ࢘ࢴࢠࡊࡒ㸣⾪ 1 ࡞ᖲ⾦ᰶ㛣㊝㞫࡛࢕࢛ࣤ໩࣎ࢷࣤࢨࣔ
ࣜࡡ⤎ᯕ࡞ࡗ࠷࡙㸡ᐁ㥺ೋ࡛භ࡞♟ࡌ㸣CASSCF࣬CASPT2 ࡡ⤎ᯕࡢ࠷ࡍࡿࡡฦᏄ࡞࠽࠷࡙ࡵ㸡ࡻࡂᐁ㥺ೋࢅ්⌟ࡊ࡙࠽ࡽ㸡┞ᑊㄵⓏ MCP ࡞ࡻࡽ㧏⢥ᗐ㞹Ꮔ≟ឺ஢ῼ࠿ᐁ⾔࡚ࡀࡾࡆ࡛࠿ฦ࠾ࡾ㸣ࡱࡒ㸡Ce, Gd, Ybࡡ୔ࡗࡡࣚࣤࢰࢼࢺ࡞㛭ࡊ࡙ࡢ㸡㞹Ꮔ≟ឺ࠿࡮࡯༟ୌ㒼⨠⌦ㄵ࡚オ㏑࡚ࡀࡾࡆ࡛࠿☔ヾ࡚ࡀࡒ㸣⾪ 1 CASSCF/MCP-tzp ࡞ࡻࡾ LnF (Ln = Ce, Gd, Yb) ࡡ㞹Ꮔ≟ឺ㸡⤎ྙ㛏࠽ࡻࡦ࢕࢛ࣤ໩࣎ࢷࣤࢨࣔࣜ⤎ྙ㛏 / ÅฦᏄ㞹Ꮔ≟ឺ୹㒼⨠CeF4Δ(4f)1(6s)1(5d)1GdF

8 -Σ

72(4f) (6s)2.005, [1.942]

YbF

2 +141a)Calc.

(4f) (6s)Σ࢕࢛ࣤ໩࣎ࢷࣤࢨࣔࣜ / eVExp.

2.077b)a)2.069, [2.005]

Exp. c)

Calc.
4.92

5.53

1.959a)5.74, [6.39]

6.16±0.07

2.016a)5.91±0.05

5.32, [6.03]a) ᣋᘴහࡡೋࡢ CASPT2/MCP-tzp㸣PT2 ゝ⟤࡞ࡢ 5s5p 㞹Ꮔ┞㛭ࡵཱིࡽ㎲ࢆ࡚࠷ࡾ㸣b) Ref. [8]㸡c) Ref. [9] LnF (Ln = Ce, Gd, Yb) ࡡ㞹Ꮔ≟ឺ࠿༟ୌ㒼⨠⌦ㄵ࡚࡮࡯オ㏑࡚ࡀࡾࡆ࡛࠿♟ࡈࡿࡒࡡ࡚㸡ᮇ◂✪ࡡࢰ࣭ࢣࢴࢹཬᚺࡡよᯊ࡞ࡢ㸡MP2/MCP-tzp (Ln) + cc-pVTZ (ࡐࡡ௙) ࢅ⏕࠷ࡾࡆ࡛࡞ࡊࡒ㸣ࡆࡆ࡚ࡢ㸡ゝ⟤⤎ᯕᚋࡼࡿࡒཬᚺ࣎ࢷࣤࢨࣔࣜ᭜㟻ࢅ㸡Yb+ ࡡሔྙ࡞ࡗ࠷࡙㸡ᅒ 2 ࡞ᶅᘟⓏ࡞♟ࡊ࡙࠷ࡾ㸣ࡱࡒ㸡྘Ꮽᏽᵋ㏸࣬㐼⛛ᵋ㏸ࡡᖼరᵋ㏸ࢅᅒ 3 ࡞♟ࡌ㸣ᵋ㏸᭩㐲໩࣬㐼⛛≟ឺ᥀⣬ࡡ⤎ᯕ㸡ᅒ 2b ࡞ぜࡼࡿࡾࡻ࠹࡞㸡Yb+ ࡞ࡻࡾ C-F ⤎ྙว᩷ཬᚺࡡ㐼⛛≟ឺࡢ㸡ࡵࡽᡬࡔᶭᵋࢅᨥᣚࡌࡾᵋ㏸ࢅࡵࡗ㸣ࡱࡒ㸡㐼⛛≟ឺ᥀⣬ࡡ⤎ᯕ㸡୔ဤ⎌୯㛣మࡢぜࡗ࠾ࡼࡍ㸡Yb+ ࡡሔྙ࡞ࡗ࠷࡙ࡢ᣼ථѸ ⬲㞫ᶭᵋࡡྊ⬗ᛮ࠿ྫྷᏽࡈࡿࡒ㸣௑ᅂࡡ MP2/MCP-tzp ࢅ⏕࠷ࡒ⤎ᯕࡢ㸡ࡆࡿࡱ࡚࡞ᥞฝࡈࡿ࡙࠷ࡾᐠᗐỏ㛭ᩐἪ࡞ᇱࡘࡂ⌦ㄵ◂✪ࡡ⤎ᯕࢅࣆ࢚࣭ࣞࡌࡾ⤎ᯕ࡚࠵ࡾ㸣ୌ᪁㸡Ce+࣬Gd+ ࡡሔྙ࡞ࡢᅒ 2b ࡞ᑊᚺࡊࡒ‵Ꮽᏽ≟ឺ㸝IM1㸞࠿ぜࡗ࠾ࡾ࡛ྜྷ᫤࡞㸡୔ဤ⎌୯㛣మ࡞ᑊᚺࡌࡾ㐼⛛≟ឺ࠿᩺ࡒ࡞ぜࡗ࠾ࡖࡒ㸣ࡆࡿࡢ㸡Ce+࣬Gd+ ࡡཬᚺᶭᵋ࠿ࡵࡽᡬࡔᶭᵋࡡࡲ࡚㐅⾔ࡌࡾ࡛ࡊ࡙࠷ࡾᐠᗐỏ㛭ᩐἪ㸠 ECP ࢅ⏕࠷ࡒ⌦ㄵ◂✪࡛␏࡝ࡽ㸡Koyanagi ࡼࡡ᭩᩺ࡡᐁ㥺ࢸ࣭ࢰࢅࣆ࢚࣭ࣞࡌࡾ⤎ᯕ࡚࠵ࡾ㸣⌟ᅹ㸡Ab initio ฦᏄ㌮㐠ゝ⟤࡛┞ᑊㄵⓏ MCP Ἢࡡ㏻ິ࡞ࡻࡽ㸡ṟࡽࡡࣚࣤࢰࢼࢺୌ౮࢕࢛ࣤ࡞ࡻࡾ C-F ⤎ྙよ㞫ཬ
ᚺᶭᵋࢅよᯊ୯࡚࠵ࡾ㸣レ⣵ࡢᙔ᪝ሒ࿈ࡌࡾ㸣(a) IM1(b) TS
1.4552.342

2.046

2.070

(d) Product (CH3 radical + Yb2+F-)(c) IM2
2.710

1.961+3.209

ᅒ 2 CH3F + Ln+ Ѝ LnF+ + CH3 ࡡཬᚺ⤊㊪୕ࡡᏭᏽ࣬㐼⛛≟ឺᵋ㏸ (in Å)㸝MP2/MCP-tzp + cc-pVTZ㸞࠘ཤ⩻ᩝ⊡࠙ [1] H. H. Cornel et al., J. Am, Chem. Soc. 118, 9960 (1996). [2] R. H. Hertwig and W. Koch, Chem. Eur. J,5, 312 (1999). [3] D. Zhang et al., J. Phys. Chem. A, 106, 4153 (2002). [4] G. K. Koyanagi et al., Int. J. Mass. Spectrom.,
241, 189 (2005). [5] (a) M. W. Schmidt et al., J. Comput. Chem. 14, 1347 (1993), (b) ฦᏄᵋ㏸⥪ྙゞㄵఌ 2006; 2E05.,[6] MCP-online library: http://meg.cube.kyushu-u.ac.jp/sapporo3/index.jsp [7] G. Karlström et al., Comput. Mat. Sci., 28,222 (2003). [8] K. P. Huber and G. H. Herzberg, MOLECULAR SPECTRA and MOLECULAR STRUCTURE IV., VAN
NOSTRAND REINHOLD COMPANY (1979). [9] L. A. Kaledin et al., J. Mol. Spectrosc., 193, 285 (1999).