Transcription of 4章．フロンティア電子論（HOMO-LUMO 相互作用の理論）
1 2013/11/20 HOMO-LUMO E R R ( ) ( ) H ckel 2222 ABABocc unoccunocc occirjsrsirjsrsABB AijijijjiCCCCE (1) r s AirC BjsC i C C C C C C C rs H ckel r s occ unocc (occupied orbital) (unoccupied orbital) (1) E (1)
2 ( rs ) (1) E D(Donor ) HOMO A(Acceptor ) LUMO (1) HOMO-LUMO D HOMO A LUMO HOMO-LUMO EHOMO-LUMO 2,,22 DAHOMO rLUMO sHOMO LUMODAHOMOLUMOCCE (2) I P1 P2 (tran- sition state.)
3 TS) TS1 TS2 TS2 TS1 ( ) P2 0 LUMOHOMODA HOMO-LUMO Total EnergyReaction CoordinateTS1TS2P1P2I ( ) Diels-Alder Diels-Alder Diels-Alder (i) Diels-Alder OOO+OOOfast (3) (ii) Diels-Alder XY+XYXYor (4) (1)(2)
4 Cir XY(iii) Deals-Alder 2,3 C-5 C-6 B C-2 C-3 A OOCNCN+CNCNOOOOCNCNA(62%)B(16%)123456 (5) A A B Diels-Alder A B Pt(PH3)2 R-H Pt(PH3)2 H-H H2Pt(PH3)2 (1) Pt(PH3)2 CH4 (CH3)(H)Pt(PH3)2 (2) (1) Enegetics HOMO-LUMO Pt(PH3)
5 2 H2 Low and Goddard III, JACS, 1984, 106, 6928. III III (kcal/mol) R ( ) I. Lewis acid - Lewis base II Pt(d10) Pt(d9s1) (H2) 6s(Pt) *(H2) 5d(Pt) Pt H H Pt H H Diels-Alder Si-C * C=C
