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4 14 (Si,Ge,Sn) 5 →5 →

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(a- )(b- )

14 ( 1 p21 )

14 1

LG ELhttp://www.chem-station.com/odos/2009/07/peterson-peterson-olefination.html

Peterson

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( )

EL

14

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2

―

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14

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p-p*

p-p*

CO2

Peterson

thanks to ( )

Si=O

Si

Ar Ar

ArAr

Ar =tBu

OMetBuN2O

Si

Ar Ar

ArAr

O

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14p p-p*

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14

Si-C

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JACS 1986, 108, 2482.

35Cl NMR Olah

Ph3C+ ClO4−

Ph3Si+ ClO4−

Ph3Si+ ClO4− + H2O

ClO4− Si

35Cl NMR

Br Si Si

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iPr3Si+[CB11H6Br5]−Et3Si+B[C6F6]−

Mes3Si+[CB11HMe5Br5]−

Si CBtBu

tBu tBuSi CB

HtBu tBu

Si CBH

tBu HSi CBH

H HCB

pyramidalizedtrigonal

bipyramidal

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14

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14

ESR X

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Me3Si

Si

SiSiMe3σSiSi

σ*SiSi

trans conformation

Me3Si

Si

Si

SiMe3

σSiSi

Me2

Me2 Me2 Me2

σ*SiC

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William S. KnowlesNobel Prize 2001

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NH3 NH sp2.90 lone pair sp2.37

PH3 PH sp3.83 lone pair sp0.95

154 (E = N, P, As, Sb, Bi)

4

E

Wittig Horner-Wadsworth-EmmonsWittig

(Z) (E)

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II p37-

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31P NMRdP −59.0

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NB

NDip Dip

P

NB

NDip Dip

PNB

NDip Dip

LiDip = 2,6-iPr2C6H3

nBuLiN

BNDip Dip

P

NB

NDip Dip

PnBu

Li(solv)n

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15

Arbuzov

15 3 3

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( ) Wittig

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16

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ss-pp

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n

n

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LUMO

STED

lone pairLUMO

16 216 2

REH (E = O,S,Se,Te)O < S < Se < TeRE− O > S > Se > TeRE− O < S < Se < Te

→→RE· O < S < Se < Te

a- (14,15 )

N OO S,Se s*C-Se C-S→

16

16

→

EtSCH2CH2Cl >> EtOCH2CH2Cl

https://sites.google.com/site/fluordoublet/( )

S CHH

Ph

σ*SC

RSH : RSeH : RTeH :

RSR : RSeR : RTeR :

RSSR : RSeSeR : RTeTeR :

16 2a-

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S C SO

H H

1) NaH2) RX3) H3O+

FAMSO(Formaldehyde Dimethyl Dithioacetal S-Oxide)

CO

HR

BnNMe3+OH–PhCHO

S C SO

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RLi→Se-Li

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R2NLi→Se a

16 2

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PEDOT/PSS : P3HT : p

ACIE 2007, 46, 4273.