2P138Ir(I)䈍䉋䈶 Ru(II)ਃຬⅣⅣ⁁䉥䊧䊐䉞䊮㍲૕䈫
C-C ⚿วᵴᕈൻ෻ᔕ䈱ℂ⺰⊛⎇ⓥ(੩ᄢ㒮Ꮏ)㩷 !⼱᧛ 㓶ᄢ, ਛየ ཅ⑲, ૒⮮ ໪ᢥ, ᭏ ⨃ᅢ䇼✜⸒䇽䉲䉪䊨䊒䊨䊕䊮䈱 C-C ⚿วᵴᕈൻ෻ᔕ(Scheme 1)䈲䇮㘻๺ C-C ⚿ว䈏䈬䈱䉋䈉䈮㊄ዻ䈫⋧੕૞↪䈚෻ᔕ䈚䈩䈇䈒䈱䈎䈫䈇䈉ὐ䈪䇮䉁䈢䇮↢ᚑ‛䈪䈅䉎䊎䊆䊥䊂䊮㍲૕䈲䊑䉺䉳䉣䊮䈮ૃ䈢౒ᓎ᭴ㅧ䉕䈫䉎䈫䈇䈉ὐ䈪ಽሶ⑼ቇ⊛䈮⥝๧䈏䉅䈢䉏䉎䇯䊎䊆䊥䊂䊮㍲૕䈲䊉䊦䊗䊦䊈䊮䈱㐿Ⅳ㊀ว෻ᔕ䈱⸅ᇦ䈫䈭䉎䈖䈫䈎䉌䇮ᔕ↪ൻቇ⊛䈮䉅㊀ⷐ䈪䈅䉎䇯䈖䈱෻ᔕ䈲৻⥸⊛䈮࿎㔍䈪䈅䉍䇮ႎ๔଀䉅㒢䉌䉏䈩䈇䉎䈏䇮Grubbs 䉌䈮䉋䈦䈩ႎ๔䈘䉏䈢 RuCl2(PPh3)2 䈮䉋䉎䉳䊐䉢䊆䊦䉲䉪䊨䊒䊨䊕䊮䈱 C-C ⚿วᵴᕈൻ෻ᔕ䈪䈲䇮Ⅳ⁁䉥䊧䊐䉞䊮䈱 C-C න⚿ว䈏ಾᢿ䈘䉏䇮䊎䊆䊥䊂䊮㍲૕䈏↢ᚑ䈜䉎 1)䇯䈚䈎䈚䇮᭴ㅧ䈏ૃ䈢 IrCl(CO)(PPh3)2 䈲䈖䈱 C-C⚿วᵴᕈൻ䉕ⴕ䉒䈭䈇 2)䇯ᧄ⎇ⓥ䈪䈲䇮Ru(II)෸䈶 Ir(I)䈱Ⅳ⁁䉥䊧䊐䉞䊮㍲૕䉕ข䉍਄䈕䇮䈠䈱 C-C ⚿วᵴᕈൻ෻ᔕ䈱ℂ⺰⊛⎇ⓥ䉕ⴕ䈇䇮෻ᔕㆊ⒟䇮෻ᔕᕈ䈱⋧㆑䈫䈠䈱ℂ↱䉕᣿䉌䈎䈮䈜䉎䇯
Scheme 1.
R=H, Me, Ph䇼⸘▚ᣇᴺ䇽㍲૕䈫䈚䈩 RuCl2(PR3)2 ෸䈶 IrCl(CO)(PR3)2 (R=H, Me, Ph)䉕䇮ၮ⾰䈫䈚䈩䉳䊐䉢䊆䊦䉲䉪䊨䊒䊨䊕䊮䈱ઍ䉒䉍䈮䉲䉪䊨䊒䊨䊕䊮䉕⸘▚䈮ណ↪䈚䈢䇯᭴ㅧᦨㆡൻ䈮䈲 DFT(B3PW91)ᴺ䉕↪䈇䇮ၮᐩ㑐ᢙ䈲 Ru 䈫Ir 䈱ౝᲖ㔚ሶ䉕᦭ലౝᲖ䊘䊁䊮䉲䊞䊦䈪⟎䈐឵䈋䇮ේሶଔ㔚ሶ䈮ኻ䈚䈩(311111/44111/411)䉕䇮Cl 䈮䈲
6-31+G(d)䉕䇮P䇮O ෸䈶Ⅳ⁁䉥䊧䊐䉞䊮䈱 C 䈮䈲 6-31G(d)䉕䇮䈠䈱ઁ䈱 C ෸䈶 H 䈮䈲 6-31G 䉕↪䈇䈢䇯䉣䊈䊦䉩䊷⹏ଔ䈮䈲 DFT(B3PW91)ᴺ෸䈶 CCSD(T)ᴺ䉕↪䈇䈢䇯䉁䈢䇮䊎䊆䊥䊂䊮㍲૕䈪䈲ᄙ㈩⟎ᕈ䈏⷗䉌䉏䉎䈖䈫䈎䉌䇮CASSCF ෸䈶 CASPT2 ⸘▚䉕ⴕ䈦䈢䇯CCSD(T)ᴺ䈮䉋䉎䉣䊈䊦䉩䊷⸘▚䈮䈲䇮
Fronteir Orbital Consistent Quantum Capping Potential (FOC-QCP)ᴺ䉕↪䈇䈢 3)䇯ၮᐩ㑐ᢙ䈲 Ru 䈫 Ir 䈱ේሶଔ㔚ሶ䈮 cc-pVTZ-PP 䉕䇮ઁ䈱ේሶ䈮䈲 cc-pVDZ 䉕↪䈇䇮Cl 䈮䈲ಽᢔ㑐ᢙ䉕ട䈋䈢䇯⸘▚䈮䈲
Gaussian 03 䉕↪䈇䈢䇯䇼⚿ᨐ䈫⠨ኤ䇽䉲䉪䊨䊒䊨䊕䊮䈏Ru䈮 !2-㈩૏
䈚 䇮 䉲 䉪 䊨 䊒 䊨 䊕 䊮 ㍲ ૕RuCl2(PMe3)2 (C3H4) 1䉕↢ᚑ䈜䉎䇯
1䈲྾ⷺ㍙ဳ᭴ㅧ䉕䈫䉍䇮䉲䉪䊨䊒䊨䊕䊮䈱C=C䈏Cl-Ru-Cl䈫ᐔⴕ䈮㈩ ૏ 䈚 䈩 䈇 䉎 䇯 䈖 䉏 䈲 䇮 C=C 䈏P-Ru-P䈫ᐔⴕ䈮㈩૏䈜䉎䈫┙૕㓚ኂ䈏ᄢ䈐䈒䈭䉎ὑ䈪䈅䉎䇯C=C⚿ว㐳䈲䇮䊐䊥䊷䈱䉲䉪䊨䊒䊨䊕䊮䈮Ყ䈼䈩0.11Å 㐳䈇䇯Ir(I)䉲䉪䊨
䊒 䊨 䊕 䊮 ㍲ ૕ IrCl(CO)(PMe3)2(C3H4) 3䈲PR3䈫䉲䉪䊨䊒䊨䊕䊮䈏equatorial㕙਄䈮䈅䉎ਃᣇਔ㍙ဳ᭴ㅧ䉕䈫䉍䇮P-Ir-P䈏ᦛ䈏䈦䈩䈇䉎䇯

Figure 1. Ru(II)㍲૕෸䈶 Ir(I)㍲૕䈱᭴ㅧᄌൻ

䈖䉏䈲P-Ir-Pⷺ䈏ᷫዋ䈜䉎䈖䈫䈮䉋䉍䇮d"゠㆏䉣䊈䊦䉩䊷䈏ਇ቟ቯ䈮䈭䉍䇮䉲䉪䊨䊒䊨䊕䊮䈻䈱"#back donation䈏ኈᤃ䈮䈭䉎ὑ䈪䈅䉎䇯䈖䈱⚿ᨐ䇮C=C⚿ว㐳䈲1䉋䉍㐳䈒䈭䈦䈩䈇䉎䇯
Ru(II)㍲૕䈪䈱ㆫ⒖⁁ᘒTS12䈪䈲䇮䉲䉪䊨䊒䊨
䊕䊮䈱C-Cන⚿ว䈲1.774 Å䈮િ㐳䈚䇮Ru-C1䈲
1.938 Å䈮⍴䈒䈭䈦䈩䈇䉎䇯↢ᚑ‛䈱䊎䊆䊥䊂䊮㍲૕2䈪䈲Ru-C1⚿ว㐳䈏TS12 䈫Ყ䈼䈩䇮䈘䉌䈮
0.11 Å ⍴䈒䈭䉍䇮ㅢᏱ䈱Ru-䉝䊦䉨䊦⚿ว䉋䉍䉅⍴䈇䇯䉁䈢䇮C1-C2⚿ว㐳䈲1.448 Å䈪䈅䉍䇮ㅢᏱ䈱C-Cන⚿ว䉋䉍䉅⍴䈒䈭䈦䈢䇯Ir(I)㍲૕䈪䈱ㆫ

Table 1. 䊎䊆䊥䊂䊮㍲૕(R=H)䈱ᵴᕈ㓚ო Ea(kcal/mol)䈍䉋䈶෻ᔕᾲ$E (kcal/mol)Ir(I)Ru(II)
MethodEa$E

Ea$E

DFT

29.5-19.6

47.3

-1.8

MP242.6-25.8

43.2-0.4

MP334.4-14.7

52.8-1.9

MP4(DQ)

36.7

-26.4

49.9

-1.7

MP4(SDQ)

32.9

-31.3

46.6

-3.4

CCSD

29.2

-30.0

48.4

-1.7

CCSD(T)

26.0

-28.9

41.1

-3.3

⒖⁁ᘒTS34䈪䈲䇮C1-C3⚿ว㐳䈏2.298 Å䈮િTable 2. 䊎䊆䊥䊂䊮㍲૕෸䈶䊑䉺䉳䉣䊮䈱⥄ὼ゠㆏䈱㐳䈚䈩䈇䉎䈏䇮䈖䉏䈲TS12䈪䈱1.774 Å䈮Ყ䈼䈩භ᦭ᢙ㕖Ᏹ䈮㐳䈇䇯䉁䈢䇮Ir-C1〒㔌䉅2.026 Å䈫䈭䉍䇮3䉋䉍䈲4䈮ㄭ䈇䇯ᓥ䈦䈩䇮TS34䈲䇮TS12䈮Ყ䈼䈩↢Ir(I)ᚑ‛ነ䉍䈱᭴ㅧ䈪䈅䉎䇯䈖䈱䈖䈫䈎䉌෻ᔕ䈲Ru(II)
Ru(II)䊑䉺䉳䉣䊮䈮Ყ䈼䈩࿎㔍䈪䈅䉎䈖䈫䈏␜ໂ䈘䉏䉎䇯↢ᚑ♽䈱䊎䊆䊥䊂䊮㍲૕䈮䈲䊑䉺䉳䉣䊮ห᭽䇮
0.061
0.066
0.067
4"*
Hartree-Fock instability䈏⷗䉌䉏䈢䇯ታ㓙䇮MP2
䈎䉌MP4(SDQ)䈻♖ᐲ䉕਄䈕䈩䉅䇮Ru(II)㍲૕䈱෻ᔕᾲ($E)䈲෼᧤䈚䈭䈇(Table 1)䇯CASSCFᴺ
0.119
0.156
0.161
3"*
䈮䉋䉎HOMO-LUMOઃㄭ䈱⥄ὼ゠㆏䈲䇮Ru(II)㍲૕䇮Ir(I)㍲૕౒䈮䊑䉺䉳䉣䊮䈱"䇮"%䈮ૃ䈩䈇
1.885
1.852
1.847
2"
䉎䇯&"䈫'"%䈱භ᦭ᢙ䈱๺䈏⚂2䈪䈅䉎䈖䈫䈎䉌䇮2"(HOMO)䈎䉌3"*(LUMO)䈻䈱ബ⿠㔚ሶ㈩⟎䈏㊀ⷐ䈪䈅䉎䈖䈫䈏␜ໂ䈘䉏䉎䇯ታ㓙䇮CASSCF
1.935
1.925
1.926
1"
ᵄേ㑐ᢙ䈮䈲䈖䈱㔚ሶ㈩⟎䈱ነਈ䈏ᄢ䈐䈇䇯⥄ὼ゠㆏䈱භ᦭ᢙ䈎䉌䇮䊎䊆䊥䊂䊮㍲૕䈲䊑䉺䉳 Table 3. RuCl2(PR3)2 ෸䈶 IrCl(CO)(PR3)2 (R=H, Me,Ph) 䈱 ᵴ ᕈ 㓚 ო Ea (kcal/mol)a) ෸ 䈶 ෻ ᔕ ᾲ $E
䉣䊮䈮Ყ䈼䇮C1-C2⚿ว䈏ᒝ䈒C2-C3⚿ว䈏ᒙ(kcal/mol)a)䈇䈖䈫䈏␜ໂ䈘䉏䉎䇯䈖䈱⚿ᨐ䈲䇮C1-C2෸䈶
HMePhC2-C3〒㔌䈮෻ᤋ䈘䉏䈩䈇䉎䇯㊄ዻ-C1〒㔌䈲 R
Ea$E
Ea$E
Ea $E
2"-3"*ബ⿠㔚ሶ㈩⟎䈱ሽ࿷䈮䉅䈎䈎䉒䉌䈝䇮ੑ Ru(II) 26.0 -28.9 27.3 -26.6 27.0 -28.8
41.1 -3.3
39.5 -4.3
38.6 -7.2㊀⚿วᕈ䈏ᱷ䉍䇮ㅢᏱ䈱㊄ዻ-䉝䊦䉨䊦⚿ว䉋䉍 Ir(I)䉅⍴䈇䇯a) CCSD(T)-calculated values
Ru(II)㍲૕䈱ᵴᕈ㓚ო(Ea)䈲䇮䊖䉴䊐䉞䊮㈩૏
ሶPR3䈮䉋䉌䈝䇮27 kcal/mol ⒟ᐲ䈪䈅䉍䇮27䌾29 kcal/mol 䈱⊒ᾲ෻ᔕ䈪䈅䉎(Table 3)䇯৻ᣇ䇮Ir(I)㍲૕䈪䈲䇮Ea䈏39~41 kcal/mol 䈫㜞䈒䇮෻ᔕᾲ䈲ዊ䈘䈇䇯䈖䈱⚿ᨐ䈲䇮Ru(II)㍲૕䈪䈲C-C⚿วᵴᕈൻ෻ᔕ䈏ㅴⴕ䈜䉎䈏䇮Ir(I)㍲૕䈪䈲ㅴⴕ䈚䈭䈇䈫䈇䈉ታ㛎⚿ᨐ䈱௑ะ䈫৻⥌䈚䈩䈇䉎䇯
Ru(II)㍲૕䈫Ir(I)㍲૕䈱෻ᔕᕈ䈱㆑䈇䈱ේ࿃䈮䈧䈇䈩䈲ᒰᣣ⊒⴫䈜䉎䇯
References and Notes
1 M. R. Gagne and R. H. Grubbs, Organometallics, 11, 3933 (1992).
2 S. T. Nguyen, L. K. Johnson, and R. H. Grubbs, J. Am. Chem. Soc. 114, 3974 (1992).
3 Y.-y. Ohnishi, Y. Nakako, H. Sato, and S. Sakaki, J. Phys. Chem. A, 112, 1946 (2008).