25

,
.
.

 .
.
: - , ,

, , . .
.

 Pd -!
Ph
H

Br

+ Li+ -SCH2CH3

Ph

SCH2CH3

Pd(PPh3)4 H

+ Li+ Br-

H
93 %

H3C

86 %

Pd P

CH3

3 4

+
Br

CH3

CH3CN, Et3N
125 C, 18

+
HBr

Et3N

PPh3

PPh3
Cl Rh PPh3
PPh3

Cl
Cl

Pt

Ph3P

Pd

PPh3

PPh3
()

NH3
NH3

-(II)
cis-platin,

H3 N
H3 N

NH3
Co
NH3

3+

NH3
NH3

(III)

 ,
Et3P

Cu
H

Cr

H
(6-)- (0)

Cl

Pd

4-()-

)-(I)

(0)

H3 C

CH3

(II)-

Fe

(II) ()

CH3

CH3
H3C Ru
H 3C
H3 C
H 3C

(5-)-

CO
CO

(1-)(-

PPh3

(3-)()-

OC

Fe

CH3

CH3
CH3
CH3

R3P
Ni
R3P

(6-)(4-

(2-)--

)(0)

()(0)



Cl

Br

CN OR H

R

R
R

R
R

R
R
R
R R
- -
, -

-1

6
8

-1

+1

-1

-1

H3N:

H2O:

R3P: (R = , )

L
L

2
2

:=O:

H2C=CH2

()

H
AcO-

X
X

2
2

R-

()

C N

LX

F-, Cl-, Br-, I-

L2X

 18 (16)

IVB (4) VB (5) VIB (6) VIIB (7)

4
5
6
7

VIIIB (8, 9, 10) 1A (11)

8

10

11

3d

Ti

Cr

Mn

Fe

4d

Zr

Nb

Mo

Tc

Ru Rh

Pd

Ag

5d

Hf

Ta

Re

Os

Pt

Au

Co Ni Cu
Ir

 Co3+(d6)
4p

4s
3d6

4p
4s
3d6

(a)

(b)

N
C

NC
d2sp3

CN
Co

NC
3d6

(c)

CN
C
N
(d)

[Co(CN)6]3-, 18- .
) Co3+.

b) .
) d2sp3 .

Cl
Cl

Pt

NH3
NH3

6p
,

dsp2
5d8

:
-
- (18e 16e )
=
+ X

2PtCl6
+4

Fe

Cl
Cl

+2

Pt

+2

NH3
NH3

PPh3
Ph3P

Pd

PPh3

PPh3
Cl Rh PPh3

PPh3

PPh3

+1

 =
dn + 2*( )
dn =

2PtCl6
dn

Cl

Fe

Cl

Pt

NH3
NH3

PPh3
Ph3P

Pd

PPh3

PPh3

Cl Rh PPh3

PPh3

PPh3

10

18

18

16

18

16

PPh3
Ni(CO)4
dn

Fe(CO)5

Cl

Pd
Cl

10

18

18

16

PPh3

1. -
2. ( )
3. ()
4.
5. -

-
Pd(PPh3)4
-

18e Pd(0)

Pd(PPh3)3 + :PPh3
-

16e Pd(0)
PPh3

PPh3
Cl Rh PPh3
PPh3
-

16e Rh(+1)

Cl

Rh PPh3 + :PPh3
-

14e Rh(+1)

 ( )

Ph3P

I
Pd

Ph3P
Pd(II)
16e

+ H3C
Ph

Ph3P
Li

CH3
Pd

Ph3P

+ LiI
Ph

Pd(II)
16e-

 ()
R Br

M(0) +

Mg(0)
Et2O

HBr

Mg

RH + MgBr2

Br

Mg(II)
X
X Y

M(II)

H H

R H SiR3

H X

R X

X X

Y
-

Ph3P PPh3
Pd
Ph3P PPh3
Pd(0)
-

18 e

Ph3P

PPh3
Pd

Ph3P
Pd(0)
16 e

Ph3P
Pd

Ph

Ph3P
Pd(0)
14 e

Ph3P Ph
Pd
I
Ph3P
Pd(II)
16 e-

Pd(II)
Br

Pd(PPh3)4
S

Ph3P
Ph3P

Pd
S
PPh3
Ph3P

Br Pd(0)

L
M:
L

Rh

PPh3 H2

Ph3P

Cl

Ph3P

Rh(I)

Ar

H
Rh H
Cl

Rh(III)

Ar
M
X

()
Ph3P
OC

CH3

Cl

Ir
I

PPh3

-
SN2 + I6

18 e Ir(III); d

H3C

Ph3P
OC

Cl
Ir
PPh3

Vaska's complex
16 e- Ir(I); d8

H2

Ph3P
OC

Ir
Cl

PPh3

18 e- Ir(III); d6

M (II)
Y

M(0) +

X
Y

. ,
, -
Ph

Ph
Pd

Ph

Ph

Me

DMSO

Me

80 C

Me

Me

Pd
Ph

Ph

Ph

Ph

-
Me
Ph

P
Ph

Ph
Pd

Me

Ph



H
Ph3P

Bu

Ni

Ph3P

CH3

Ni(II)
16 ePh3P

PPh3
Pd
R
N
H

Pd(II)

Ph3P

Bu

Ni

H3C

Ph3P

Ni(0)
14 eR

SiMe3

SiMe3 +
N
H

(Ph3P)2PdL2
Pd(0)

Pd(PPh3)3

Pd(PPh3)4

Pd(PPh3)2
+
PPh3

+
PPh3
H

Pd(PPh3)2 +
Br

Ph

H
Ph3P
Ph3P

Pd
Br

Ph
EtSLi

H
Ph3P

EtS
+

Ph
Pd(PPh3)2

Ph3P Pd
EtS

H
H
Ph

X
M
Y

L = R3P, CO

X M Y
Y
M-X.

CO
R

+L
Ln+1M

-L

CH3

Mn (I)
18 e-

LnM

CO

(OC)4Mn

CH3
1,1

(OC)4Mn

CO

R
CH3
(OC)5Mn

O
Mn (I)
16 e-

O
Mn (I)
18 e-

 , R = H
+L

LnM

-L

R
Ar
Br

Pd
PPh3

Ln+1M

Ar

CH2
CH2 1,2

Br

Pd
PPh3

Pd (II)
16 e-

PPh3

PPh3
Br Pd
PPh3
Pd (II)
16 e-

Pd (II)
14 eAr
Br

Pd
PPh3

CH2
CH2

Ar
Br

Pd
PPh3

Ar

H
Br

Ph

Ph

H
Pd

Br
Pd

PPh3

PPh3
Pd(II)
14 e

Pd(II)
16 e-

H
Br

Pd

Ph
-

H
Br

Pd
PPh3

PPh3
Pd(II)
14 e

Pd(II)
14 e

Ph

H
Br

Ph

Pd
PPh3
Pd(II)
16 e
-

H3C
Pd P

CH3

3 4

+
Br

CH3

CH3CN, Et3N
125 C, 18

86 %
+
HBr

Et3N

L
Pd L

L +

2L+ L

Pd

18

16

R
R1 +

R2

-L

Pd(II)

Pd(0)

Pd X
L
Pd(II)

R2
C -

Pd X
R1

L
+L

R2
L Pd L

Pd X

R1

14

Pd X

Pd

R1

Pd X -H
L
Pd(II)

R2
X

Pd L
R1

L
Pd(II)

H
X +

Pd(0)

R1

B*HX
Pd(0)

+ H X

R2

R1

PdL2
(14e)

R1

H
(16e)

L2Pd

Pd(II) L2Pd

Pd(II)

X
-H

R2

(16e)

L2Pd
1

(16e)

X
H
R2

H Pd(II)

R2

1% Pd(OAc)2
Br +

+
OTf

2% PdAr3

(o-Tol)3P 20 mol %
NHCbz
K2CO3, DMF, Bu4NCl

CO2R
CbzHN
77 %

Pd(OAc)2 5 mol %
OEt

CO2R Pd(OAc)2 10 mol %

Br

(o-Tol)3P 20 mol %
Et3N, DMF

CO2Et
87 %

I
+

Pd(OAc)2 (.)
Et3N, DMF
15 . 100 C
PPh3
72 %

I
Ph
I

Pd

-1,2-

PPh3

Ph3P

Pd
Ar

Pd
-
-
L
H

Pd

I
H

H
L

Pd
I

H
H