2019 @Main Group Chemistry

1,2

13,1415,16

17

( ) ( ) I

2ISBN; 9784807908202

( ) ( )

ISBN; 9784807905874W. Henderson( ) ( )

( )ISBN: 9784759810042

( ) (11)

( ) ISBN:9784000110419

Dmitri Mendeleev

Periodic Table of Elements

(period)

the 1stthe 2ndthe 3rd

(group)

(Main Group Element)

11,12

Ionization Energy (IE) =

E(g) → E+(g) + e− DH

IEIE

2 (ns2) 13 (ns2np1) IE →15 (ns2np3) 16 (ns2np4) IE →

11ISBN 978-4000110419

2 13

15 16

Electron Affinity =

E(g) + e− → E−(g) DH

Emsley, J., The Elements; Oxford University Press: New York, 1998.

0 or17 ( )

1 (ns1) 14 (ns2np2) EA→

0

50

100

150

200

250

300

350

400

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35

(kJ/

mol

)

H

He

Li

Be

B

C

N

O

F

Ne

Na

MgAl

Si

P

S

Cl

Ar

K

Ca

Sc

Ti

VCr

Mn Fe

CoNi Cu

ZnGa

Ge

As

Se

Br

Kr

Linus C. PaulingNobel Prize1954

Electronegativity =

11ISBN 978-4000110419

PaulingMullikenAllred Rochow

(covalent radius)→→

→→

→

Online Textbook: Atomic Structure and the Periodic Tablehttp://www.chem1.com/acad/webtext/atoms/index.html

WebElements: the periodic table on the webhttp://www.webelements.com/

Albert EinsteinNobel Prize1921

m0 vm (c= )

Pyykko, P., Chem. Rev. 1988, 88, 563-594.

―

ISBN 978-4807913442

a0a0

e0: , ħ: Planck , me: , e:

4 p e0 ħ

[v=Zc/137; Z= ]

4f 5d 6p

→

1s2s 2p3s 3p 3d4s 4p 4d 4f5s 5p 5d 5f 5g6s 6p 6d 6f 6g 6h7s 7p 7d 7f 7g 7h

ns

np

ns

np

ns

np

ns

np2s,2p3s,3p3s,4s

→5s 6s

→

Pyykko, P., Chem. Rev. 1988, 88, 563-594.

―

ISBN 978-4807913442

→

―

ISBN 978-4807913442

2s 2p sp ns np sp

= 1s 2yb ya

11ISBN 978-4000110419

p

ps, s* p, p*

2 2→

( )

(= )

Pauling

X M

I p302

Xδ– Cδ+

X = N, O, F, Cl, (S,) Se, Br, (I)Mδ+ Cδ–

M =

(1)

(oxidation #)

= =

= 2 2 2

=

1. +1 −12.

=(1) +1 ( : NH4

+)(2) ( : CMe4)(3) ( : CH2Cl2)

Parkin, G., J. Chem. Edu. 2006, 83, 791-799.

(valency, valence)

Karen, P.; McArdle, P.; Takats, J., Toward a comprehensive definition of oxidation state (IUPAC Technical Report). In Pure Appl. Chem., 2014; Vol. 86, p 1017.

(2)

Parkin, G., J. Chem. Edu. 2006, 83, 791-799.

(# of bonds)

(coordination #)

= 2 2

=

2 2, 3 3

=

=

VSEPR

(valence shell electron pair repulsion rule)

W. Henderson( ) ( )( )

→1) Lewis2) p 13) 4)

LP >LP BP>BP(LP: lone pair, BP: bonding pair)

SF4

(hypervalent compounds)=

PF5(1) (eq) sp2

(2) (ap) pp

3 4(3) eq ap

―

ISBN 978-4807913442 Chemistry of Hypervalent CompoundsKin-ya Akiba Ed., Wiley-VCH, 1999

William LipscombNobel Prize1976

Be(CH3)2

CH5+ B2H6

W. Henderson( ) ( )( )

―

ISBN 978-4807913442

I p303

Charles PedersenNobel Prize

1987

→( p10 )

sp3

( )

sp3

=

TlCl, SnCl2, PbCl2, GeCl2(dioxane)

TlR, PbR2

14

―

ISBN 978-4807913442

ener

gyen

ergy

2s

2psp3 sp3

C(no hybridization)

CX4(sp3)

C(sp3)

ΔEprom

ΔEbond

ener

gyen

ergy

ns

npsp3 sp3

E(no hybridization)

E(sp3)

EX4(sp3)

ns

np

EX2(no hybridization)

ΔEprom ΔEbond

Science 1981, 214, 1343-1344.

J. Am. Chem. Soc. 1981, 103, 4587-4589.

Science 2004, 305, 1755-1757.R = 2,4,6-Me3C6H2

R = 2,4,6-tBu3C6H2

R = Si(CHSiMe3)2iPr

―

ISBN 978-4807913442

Wittig

b-

I p343-347

Georg WittigNobel Prize

1979

P CHH

PhPh

Ph

σ*PC

C CRR

RR

R3Si

σSiC

C N

σCN

σ*CN

2p 2pC

P

σCP

σ*CP

2p3p