4P112
ࡔ࠲ࡠ࠮ࡦဳ㍲૕⸅ᇦߩࡔ࠲࠮ࠪࠬ෻ᔕߦ㑐ߔࠆℂ⺰⊛⎇ⓥ㧔੩ᄢ㒮Ꮏ†‫⑔ޔ‬੗࠮‡㧕 ‫ޚ‬㕍ᧁാม†‫ޔ‬᎑↰ஜ৻†‫ޔ‬ਛየཅ⑲†‫ޔ‬૒⮮໪ᢥ†‫ޔ‬᭏ ⨃ᅢ†, ‡‫ߦ┵ᧃ ޤ⸒✜ޣ‬䉝䊚䊮ၮ䉕䉅䈧䊘䊥䉥䊧䊐䉞䊮䈲䇮ක⮎ਛ㑆૕䉇䉟䉥䊮੤឵᮸⢽䈭䈬ᐢ䈇᦭↪ᕈ䉕ᜬ䈦䈩䈇䉎䇯ߎߩࠃ߁ߥᯏ⢻ᕈࡐ࡝ࠝ࡟ࡈࠖࡦߩวᚑᴺߩ৻ߟߣߒߡ‫ޔ‬ቭ⢻ၮࠍ᦭ߔࠆㅪ㎮⒖േ೷ࠍ૶
↪ߔࠆᣇᴺ߇޽ࠆ=? (Scheme 1)‫ޕ‬ੑ⚖ࠕࡒࡦࠍㅪ㎮⒖േ೷ߣߒߡ૶↪ߒߚ࡜ࡦ࠲ࡁࠗ࠼㍲૕ߦࠃࠆࠛ࠴࡟ࡦ㊀ว෻ᔕߩ଀ࠍ Scheme 1ߦ␜ߔ‫ޕ‬step 2 ߢߪࠛ࠴࡟ࡦߩᝌ౉ߦࠃߞߡࡐ࡝ࡑ࡯㎮߇િ㐳ߒ‫ޔ‬step 3 ߢߪࠕࡒࡦߦࠃࠆ㊄ዻ-ࡐ࡝ࡑ࡯⚿ว߳ߩࡊࡠ࠻ࡁ
࡝ࠪࠬߦࠃߞߡ‫ޔ‬ቭ⢻ၮࠍ߽ߟࡐ࡝ࡑ࡯߇↢ᚑߒ‫ޔ‬หᤨߦᵴᕈ⒳߇ౣ↢ߐࠇࠆ‫ޕ‬Step 3 ߪ 4 ਛᔃߩࡔ࠲࠮ࠪࠬ෻ᔕߢ޽ࠅ‫⓸ޔ‬1⚛-᳓⚛㑆ߣ㊄ዻ-!὇⚛㑆ߩ"⚿ว߇ಾᢿߐࠇ‫ޔ‬ᣂߚߦ㊄ዻ-⓸⚛‫ޔ‬

Step 1

Step 3὇⚛-᳓⚛㑆ߩ"⚿ว߇↢ᚑߔࠆ‫ޕ‬ᧄ⎇ⓥߢߪ‫ ߩߎޔ‬step 2ߣ step 3ߩ㔚ሶ⊛ㆊ⒟ࠍℂ⺰⊛⎇ⓥߦࠃߞߡ᣿ࠄ߆ߦߒ‫ࠬࠪ࠮࠲ࡔޔ‬෻ᔕߩ೙ᓮߩℂ⺰⊛੍᷹ࠍ⹜
3ߺߚ‫ޕ‬2Step 2‫▚⸘ޣ‬ᣇᴺ‫ ޤ‬᭴ㅧᦨㆡൻߪ B3PW91 ᳢㑐ᢙࠍ↪޿ߚ DFTᴺScheme 1ߢⴕ޿‫࡯ࠡ࡞ࡀࠛޔ‬ᄌൻߪ MP4(SDQ)ᴺߢⴕߞߚ‫ޕ‬ၮᐩ㑐ᢙߣߒߡ Sc‫ޔ‬Ti‫ޔ‬Y‫ޔ‬Zr‫ޔ‬La‫ޔ‬Hf ߪౝᲖ㔚ሶ䉕 Christiansen 䈱᦭ലౝᩭ䊘䊁䊮䉲䊞䊦=?䈪⟎䈐឵䈋䇮ଔ㔚ሶ䉕 (541/541/211)䈪⸥ㅀ䈚䈢=?=?䇯
H䇮C䇮N䇮F䇮Si 䈮䈲 6-31G*ࠍ૶↪ߒ‫ޔ‬N ߦߪߐࠄߦಽᭂ㑐ᢙࠍട߃ߚ‫ޔߒߛߚޕ‬Cp*ਛ䈱䊜䉼䊦ၮ䈱 C 䈮䈲 6-31G ࠍ↪޿ߚ‫ ߡߒߣ࡞࠺ࡕ▚⸘ޕ‬Cp*2La(CH2CH2NR2) 2 (Cp* = C5Me5; R = CH3,SiH3, orCF3)ࠍណ↪ߒߚ‫ ߡోߪ▚⸘ߩࠄࠇߎޕ‬Gaussian 03 ߢⴕߞߚ‫ޕ‬‫⚿ޣ‬ᨐߣ⠨ኤ‫ ޤ‬2 ߦࠛ࠴࡟ࡦ߇ᝌ౉ߔࠆ step 2 ߢߪ‫ࡦ࡟࠴ࠛߕ߹ޔ‬㍲૕ Aet ߇ᒻᚑߐࠇࠆ‫ޕ‬Aetߦ߅޿ߡ La ߣ C ߩ〒㔌ߪ 3Å એ਄㔌ࠇߡ߅ࠅ‫ߩࡦ࡟࠴ࠛޔ‬㈩૏ߪߘࠇ߶ߤᒝߊߥ޿ (Table 1)‫ޕ‬߹ߚ 1 ߢߪ H#ߣ La ߩ㑆ߦ agostic ⋧੕૞↪߇ᒻᚑߐࠇߡ޿ࠆ߇‫⋧ߩߎޔ‬੕૞↪ߪࠛ࠴࡟ࡦߩ㈩૏
ߦࠃࠅಾᢿߐࠇࠆ‫ޕ‬ㆫ⒖⁁ᘒ TSEt ߢߪ La-C ⚿ว(2.616 Å)ߪ߶߷ᒻᚑߐࠇߡ޿ࠆ߇‫ߣࡦ࡟࠴ࠛޔ‬ࠕ࡞ࠠ࡞ߩ C-C 㑆ߪ 2.101 Å ߢ޽ࠅ‫ޔ‬߹ߛ㔌ࠇߡ޿ࠆ‫ޕ‬H#-agostic ⋧੕૞↪ߪౣ߮ᒻᚑߐࠇߡ߅ࠅ‫ޔ‬ߎࠇߦࠃߞߡ TSet ߇቟ቯൻߐࠇߡ޿ࠆߣ⠨߃ࠄࠇࠆ‫↢ߚ߹ޕ‬ᚑ‛ Bet ߢ߽ H#-agostic ⋧੕૞↪ߪሽ࿷ߔࠆ‫ޕ‬ᵴᕈ㓚ო Ea ࠍㆫ⒖⁁ᘒߣࠛ࠴࡟ࡦ೨㚟
Table 1. step 2 ߢߩࠛ࠴࡟ࡦ㈩૏ߩ⚿วࠛࡀ࡞ࠡ
࡯ (BE) ‫ޔ‬ᵴᕈ㓚ო (Ea)߅ࠃ߮෻ᔕᾲ ($E)↢ᚑ‛ߩࠛࡀ࡞ࠡ࡯Ꮕߢߘࠇߙࠇቯ⟵ߒߚ‫ޕ‬Ea ‫ޔ‬
RBE
Ea
$E
CH-12.6
15.6
-26.5
3
$E ߣ߽ߦࠕࡒࡦߩ⟎឵ၮ߳ߩଐሽߪዊߐߊ‫ޔ‬3SiH3-14.6
17.8-24.8
kcal/mol એਅߢ޽ߞߚ(Table 1)‫ޕ‬CF3-10.514.8-24.9
MP4(SDQ)/ kcal mol-1㍲૕ߣߩࠛࡀ࡞ࠡ࡯Ꮕߢ‫ޔ‬෻ᔕᾲ$E ࠍ෻ᔕᾲߣ㪈㪅㪊㪊㪏㩷㪉㪅㪊㪇㪊㩷㪊㪅㪊㪍㪋㩷㪊㪅㪋㪌㪇㩷㪉㪅㪍㪈㪍㩷㪈㪅㪋㪈㪏㩷㪉㪅㪌㪌㪈㩷㪉㪅㪈㪇㪈㩷㪈㪅㪌㪉㪊㩷㪉㪅㪏㪇㪋㩷+ CH2=CH22 + ethyrene㪉㪅㪌㪐㪊㩷Aet㪉㪅㪍㪊㪏㩷㪉㪅㪌㪈㪇㩷

TSetFigure 1.ࠛ࠴࡟ࡦᝌ౉෻ᔕ㧔step2㧕ߢߩ᭴ㅧᄌ

Betㅪ㎮⒖േ෻ᔕߦ߅޿ߡ߽‫ޔ‬೨㚟㍲૕ Aam ߇ᒻᚑߐࠇࠆ‫ޕ‬Aam ߢߪ‫⟎ߩࡦࡒࠕޔ‬឵ၮߪੑߟߩ Cp*Ⅳߣᐔⴕߦ૏⟎ߒߡ޿ࠆ‫ޕ‬ㆫ⒖⁁ᘒ
TSam ߢ‫⚿ߦ⚛⓸ߪࡦࡒࠕޔ‬วߒߚ H ߇ La ߣ⚿วߒߚ C ߩᣇะߦะߊࠃ߁ߦ࿁ォߔࠆ‫ߎޕ‬ߩ᭴ㅧߢߪࠕࡒࡦߩ⟎឵ၮߣ Cp*Ⅳߪㄟߺวߞߞߡ߅ࠅ‫ߚ߹ޔ‬⒖േߔࠆ᳓⚛ߩᱜ㔚⩄ߪᷫዋߒߡ޿ߚ‫↢ޕ‬ᚑߔࠆࠕ࡞ࠠ࡞ࠕࡒࡦߪ㊄ዻਛᔃߣ⋧੕૞↪ߖߕ‫ޔ‬ㆆ㔌ߒߡ޿ߊߣ⠨߃ࠄࠇࠆ‫ޕ‬Ea ‫ޔ‬$E ࠍᲧセߔࠆߣࠕࡒࡦ⟎឵ၮߦࠃࠅᄢ߈ߊ⇣ߥࠅ‫ޔ‬R = CH3 < SiH3 < CF3 ߩ

Table 2.ࠕࡒࡦߣߩࡔ࠲࠮ࠪࠬ෻ᔕߢߩࠛ࠴࡟ࡦ㈩૏ߩ⚿วࠛࡀ࡞ࠡ࡯ (BE) ‫ޔ‬ᵴᕈ㓚ო (Ea)߅ࠃ߮෻ᔕᾲ ($E)
RBEEa
$E
CH3-27.2
23.6-25.2
SiH3-22.7
15.1-44.6
CF3-23.3
2.9-67.3
MP4(SDQ)/ kcal mol-1
Table 3. ⚿ว⸃㔌ࠛࡀ࡞ࠡ࡯ (BDX-Y)
RBDN-H
BDLa-C BDLa-N BDC-H
$BDa)
CH3
137.4
60.1
118.6
100.1
-21.1
SiH3
116.9
62.1
121.3
100.7
-43.1
CF3146.3
64.7
170.6
101.3-61.0a)$BD = (BDN-H㧗BDLa-C)㧙(BDLa-N㧗BDC-H),
MP4(SDQ)/ kcal mol-1

㗅ߦ෻ᔕ߇ኈᤃߣߥࠆ(Table 2)‫ࠄ߆ߣߎߩߎޕ‬ᐔဋಽሶ㊂ߩ೙ᓮߪ step 3 ߢน⢻ߢ޽ࠆߎߣ߇ࠊ߆
ࠆ‫ޕ‬㪉㪅㪎㪐㪏㩷㪉㪅㪍㪇㪇㩷+ amineAam2 + amine㪉㪅㪊㪎㪍㩷㪈㪅㪊㪈㪋㩷㪈㪅㪋㪊㪇㩷㪉㪅㪌㪈㪍㩷㪉㪅㪊㪇㪊㩷TSam㪉㪅㪐㪈㪇㩷+ CH3CH2NR2BamFigure 2. ࠕࡒࡦߣߩࡔ࠲࠮ࠪࠬ෻ᔕ㧔step 3㧕ߢߩ᭴ㅧᄌൻ
Step 2 ߢߪ La-C ⚿วߣ C=C ੑ㊀⚿ว߇ಾᢿߐࠇ‫ޔ‬La-C ⚿วߣੑߟߩ C-C න⚿ว߇ᒻᚑߐࠇࠆ‫⚿ߩࠄࠇߎޕ‬วߪߔߴߡᧃ┵ߩࠕࡒࡦ߆ࠄ㔌ࠇߡ߅ࠅ‫⚿ߩࠄࠇߎޔ‬วߩ⸃㔌ࠛࡀ࡞ࠡ࡯ߪࠕࡒࡦߩ⟎឵ၮߦࠃࠆᓇ㗀߇ዊߐ޿‫৻ޕ‬ᣇ‫ޔ‬step 3 ߢߪ N-H ⚿ว߇ಾᢿߐࠇ‫ޔ‬La-N ⚿ว߇ᣂߚߦᒻᚑ
ߐࠇࠆ‫⚿ߩࠄࠇߎޕ‬ว⸃㔌ࠛࡀ࡞ࠡ࡯ߩᄢ߈ߐߪ‫⟎ߩࡦࡒࠕޔ‬឵ၮߦᄢ߈ߊଐሽߔࠆ(Table 3)‫↢ޕ‬ᚑ‛ߩ⚿ว⸃㔌ࠛࡀ࡞ࠡ࡯ߩ๺߆ࠄ෻ᔕ‛ߩߘࠇࠍᒁ޿ߚ୯ࠍ$BD ߣቯ⟵ߔࠆ‫ޕ‬Table 2 ߣ Table 3ߦ␜ߔࠃ߁ߦ‫ޔ‬$BD ߇ᷫዋߔࠆߣ‫ޔ‬Ea ߩ୯߽ዊߐߊߥߞߡ޿ࠆ‫⟎ޕ‬឵ၮߦࠃࠆ$BD ߩᏅߪਥߣߒߡ⚿ว⸃㔌ࠛࡀ࡞ࠡ࡯BDLa-N ߣ BDN-H ߦࠃߞߡ↢ߓߡ޿ࠆ‫ޕ‬ᓥߞߡ‫ࠄࠇߎޔ‬ੑߟߩ⚿ว⸃㔌ࠛࡀ࡞ࠡ࡯ߩᄢ߈ߐ߇ step 3 ߩᵴᕈ㓚ოߩ᳿ቯ࿃ሶߢ޽ࠅ‫ࠬࠪ࠮࠲ࡔߢߣߎࠆߔ▵⺞ࠍࠄࠇߎޔ‬෻ᔕࠍ೙ᓮߢ߈ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬ਛᔃ㊄ዻࠍᄌᦝߒ‫╙ޔ‬㧟ᣖߣ╙㧠ᣖߩㆫ⒖㊄ዻ㍲૕ߩ෻ᔕᕈࠍᲧセߒߚߣߎࠈ‫ߩࡦ࡟࠴ࠛޔ‬ᝌ౉෻ᔕߢߪ╙㧟ᣖㆫ⒖㊄ዻ㍲૕ߩᣇ߇‫ࠬࠪ࠮࠲ࡔߩߣࡦࡒࠕޔ‬෻ᔕߢߪ╙㧠ᣖㆫ⒖㊄ዻ㍲૕ߩᣇ߇ Ea ߩ୯߇ᄢ߈ߊߥߞߚ‫ޕ‬ߎߩ⚿ᨐ߽෻ᔕ೨ᓟߢߩ⚿ว⸃㔌ࠛࡀ࡞ࠡ࡯ߩᏅߣࠃߊ৻⥌ߒߡ޿ߚ‫ޕ‬߹ߚหߓᣖߩౝߢߪ೨๟ᦼ߶ߤࠛ࠴࡟ࡦ㍲૕ߢߩ቟ቯൻ߇ዊߐߊߥࠅ‫ޔ‬step 2 ߩ Ea ߇ዊߐߊߥߞߚ‫╙ޔࠄ߆ߣߎߩࠄࠇߎޕ‬㧟ᣖࠃࠅ߽╙  ᣖㆫ⒖㊄ዻ㍲૕ߩᣇ߇‫ߚ߹ޔ‬೨๟ᦼߩㆫ⒖㊄ዻ㍲૕ߩᣇ߇‫ࠬࠪ࠮࠲ࡔޔ‬෻ᔕ߇⿠ߎࠅߦߊߊ‫ޔ‬㐳㎮ߩࡐ࡝ࡑ࡯߇↢ᚑߒ߿ߔ޿ߣ⠨߃ࠄࠇࠆ‫ޕ‬‫ޣ‬ෳ⠨ᢥ₂‫ޤ‬[1] Smruti B. Amin; Tobin J. Marks J. Am. Chem. Soc. 2007, 129, 10102.
[2] R.B. Ross; J.M. Powers; T. Atashroo; W.C. Ermler; L.A. LaJohn; P.A. Christiansen J. Chem. Phys. 1990,93, 6654.
[3] Marc Couty; Michael B. Hall Journal of Computational Chemistry 1996 17 1359