10- 2 437

10-3

n S L
v4+ 2 173 3.00 1 .7 '"'-' 1.8

Cu 2 1.73 3.00 1.7 '"'-'2.2

v3+ 2
’ 3 2.83 4.47 2.6'"'-'2.8
Ni 2+
4
2 11
3 2.83 4.47 2.8'"'-' 4 .0
Cr 3+ 3 3 3.87 5.20 '"'-'3.8
C0 2+ 3 3 3.87 5.20 4. 1 '"'-'5.2
2+
Fe 4 2 2 4.90 5.48 51'"'-'5.5
U] ; %
4 2 4.90 5.48 '"'-'5 .4
Mn
5 O 5.92 5.92 '"'-'5.9
%3+
5 O 5.92 5.92 '"'-'5.9

F. A Cotton and G Wilkinson, Advanced Inorganic Chemistry, 4th ed. , Wiley, New York, 1980, pp 627-628
Bohr

10- 1 - 4

10-2 10- 2 - 1

orbital)
438 11:

orbital

(many-

Huckel

bond field
filed
of angular overla

10-2-2

8 G. O. Spessard and G. L. Miessler, Organometallic Chemistry,

Oxford University Press, New York, 2010, pp. 42-4 9
9 L. Pauling, The Nature 01 the Chemical Bond, 3rd ed., Cornell University Press, Ithaca , NY, 1960, Chapter 5
 10- 2 439

••••• •••• •• •• •• •• -----

•• •• •• •• ••
-----
•• •• •• ••
3d 4s 4p 4d 3d 4s 4p Ss
| (0 1"
(P Sp 3 (PS p 3

•- -
• -
• -
• -
• •• •• •••• ••••
---- -
••••••• •• •• •• •• ••••
-----
3d 45 4p 4d 3d 45 4p 4d

Sp 3(p Sp 3(p

10-2 d2sp3

(inner orbital, 3d) orbital, 4d)

Fe(III)
1

10
B. N . Figgis and R. S. J. Che l/l. 50c. , 1959, 338; J. S. Griffith and 1. E. Orge l, Q. Rev. Chem. 50c. ,
1957, XI, 381
11
440 11 :

ta tic

dxZt
octahedron

1.2 +0.6 Ào X 2 = +1.2Ào7].

Field Stabilization En ergy, CFSE)

12 H. Bethe, Ann. Phys ., 1929, 3, 133

13 J. H. Van Vleck, J. Chem. Phys. , 1935, 3, 807
 10- 3 441

eg
/
/
/
/
/
/
/
/
/
/
/
/

AO
--- --- --- --- ---

\ I

-- --- --- --- --- ‘ _ ,-

- _ ___ t

10-3

Field Stabilization Energy,

10-3

10-3-1
U

14 J. 5. Griffith and L. E. Orgel, Q. Rev. Chel1l. 50c., 1957, XI, 381

442 11

10- 4 z
y

x x

dx 2 _

o
0 11

U O ...:L-,e>

NH 3
i F•I{
/
•

10- 4

Oh E 8C3 6C2 6 C4 3C2 (= C/ ) 65 4 85 6 3a h 6s d

A 1g
A 2g
Eg 2 0 0 2 2 0 2 O
T1g 3 O 3 0 (R x, Ry, Rz) (2z 2 - X
2
- 1 , - 1)
T2g 3 O 3 O (xy , xz , yZ)
A 1u
A 2u
Eu 2 0 O 2 -2 0 2 O
T1u 3 O 3 O (x , y , z)
T2u 3 O -3 0
 10- 3 443

Oh E 8C3 6C2 6C4 3C2(=C/> 654 85 6 3Uh 6Sd

r (T 6 0 O 2 2 0 O O 4 2

Oh E 8C3 6C2 6C4 3C2(=C/> 654 85 6 3Uh 6s d

A 1g
T1u 3 O -3 0 (x , y, z)

Eg 2 0 O 2 2 o 2 O (2Z2 -;(2 -1 , ;(2 -1)

10-4
A 1g + T 1u +

dZ2
U T 2g
d xy' d yz' d xz
dyz'

A 1g

S, p,
444 11:

10-5
e “*
'"
‘
// I A

1- 0

d.- ---: .- - - {- - - - - -....L -t \\

E T ‘
g • 2g \ .- - - .- ----.;::--- - . :--- - - , - (T

[,l u a , //
'"""lg E
L.J
g
T ,l u
..I.
Al
'1 g

/
/
\ /

- -'e /

M ML6 6L (a- )

dXyl dyv U

[Ni(H 20)6l 2+
egl
2
Ni +

[Ni(H20)6l 2+

15
 10- 3 445
-@
10.6
5
‘‘
‘‘
, ---.
A 4p - - ---,
/
‘
T, ‘ " e'l g
(cr*)\
‘ ‘
Cotton , Chemical Application
Theory, 3rd ed. , ‘ ‘‘
\Niley-I nterscience , New York, ‘
‘\ , ' / ‘ ‘‘
1990 , /‘
/

/ eg (cr*)
4s ---, '
A, \
‘“
lg N ‘1 ‘‘
/
A ‘
‘‘ 0

\, '
/\ ‘
,'\“ “1 ‘‘
‘ ‘‘‘‘
3d _ _“ .l\ ____ _________ __
r T “ r
“ g ““ ’ 2g
“

“ “ ‘ ‘
““
l

‘‘ ‘\\‘
‘

‘‘ ‘‘
‘ -
‘‘
1
-
‘-
‘‘ %
\
\
-
1
\
“
‘1
‘‘ /
‘‘
‘‘ //
/
‘
,
\ t lll (cr) /
/

/
/

1:!:.- /
/
/

‘
l tg /
/

a lg (cr)
M/+ MX 6"-6

2
446 11

I
10- 7 Z

system) x
y

x
y
Y
z

x
X
y
z
x

co

Oh E 8C3 6C2 6C4 3C2(=C/> 654 85 6 3Uh 6Sd

12 O O O -4 o 0 0 O O

T 1g + T2g + T1II +

oh 8 C3 6C2 6C4 3C2 (=C/> 654 85 6 3Uh 6Sd

-g
o -1 -1 3 0 -1 -1
9 nu 3 nu
(xy , yz , yz)
nU 4[ nu
u (x , y , z)
nU nU
U

10-5
T 19 + T 2g + T 111 +T

T 2g dxz1 dyz )
 10-3 447

T2g

t2g

egl t lrJ

10-8

==

{
*?
/

/////- {•
||F

l
•
-
E= -
‘ • -]

-F

%
M ML6 6L
448 11

10-9).

dyz1
t2g

10-9
{r

- -
?i p

/
)
m

-“‘

2s
-
2 C5

C CN N
 10-3 449

10-10
d, p

OQPCJ
dyZ O
OQP CJ
CJOO Pz
OCJO

(bond
M -• L)
d

L -• M)

- • M

U
450 11:

10-11

-
5g
!

‘ T ‘ -
*eg
eg

Ao
A
•
‘ {
‘
1

‘3
//
/// -
U

/
L
I

hp

(a) (b)

10-3-2
 10- 3 451

d3

spin)

• Ll o •

Coulomb energy)
Coulomb
I1 Ct I1 e)
I1 c

d5

d6
• 4 • 5

1-2, 1-3, 2-3 , 4-5

• l• 1 • 2 • 3

• l• l • 2• 2 • 3• 3
1-2, 1-3, 2-3 1-2, 1-3, 2-3

10-6
d5
452 11 :

10-5

• • •

/:"0
• • • • • • • • • • • •

dl d2 d3 d4 d5

• • • • • • •• • •• ••
AO
•• • • •• •• • •• •• •• •• •• •• •• •• ••

é d7 d8 d9 (/ 10

Ao
• • • • • • •• • • •• •• •

dl d2 d3 ,, 4 d5

• • • •• • •• ••

AO
•• •• •• •• •• •• •• N •• •• •• •• •• •• ••

d6 d7 é d9 d lO

pairing en ergy,

J1 0 >
 1C• 3 453

Ll o <

[Co(H 20)6]3+

2+ 3+
5
d

10-6

lon H lon n
d 1 Ti 3+ 18.800
2
d 18 ,4 00
d3 v 2+ 12 ,300 Cr 3+ 17 ,4 00
cf Cr 2+ 9 ,2 50 23 , 500 Mn 3+ 15.800 28 ,000
d 5 Mn 2+ 7.850 b
25.500 Fe 3+ 14 , 000 30 , 000
rf' Fe 2+ 9 , 350 17 , 600 C0 3+ 16 ,7 50 21 ,000
d7 C0 2+ 8 ,4 00 22 , 500 Ni 3+ 27.000
d8 Ni2+ 8 , 600
CP Cu 2+ 7 ,850
d10 Zn2+ O

D. A P. G. Chem. , 1995, 34, 5666; D .A.

P. G. Inorg. Chem ., 1999, 38, 4949. T. M. DUJl e, D. S. Mc Cl ure , R. G
Some Aspects of Crystal Field Haper & Row , New York, 1965 D. S.
Th e Effects of Inner-orbitals on Thermodynamic Properis
a cm - 1
454 11 ’

•
eg cg

• • • •
t2g
,
- - - ‘ 28

dl d4
10 -12

10- 3- 3
Field Stabilization Energy, (1)

d4

g
LFSE
3( Ao) = -g

10-7

(pairing)
LFSE

2+

16 F. A. Cotton, J. Chem. Educ. , 1964, 41 , 466

 10- 3 455

10-7

LFSE Coulombic
t 2g eg {Åo}
• 2-
l 5
•| • 4-5
2 1
I1 e
•| •| • 6
3 1 •
5 3 I1 e
• *! • • 3-
4 1 1 1 5 3 I1 e
• • • • • 0
5 1 1 1 1 1 4 I1 e
• • • • 2
6 1 1 1 l •
5 I1 c 4 I1 e
• • • 4-5
7 1 1 l 2 I1 c SI1 e
• • 6
8 1 1 •
5 3 I1 c 7 I1 e
• 3-
9 1 5 4 I1 c 7 I1 e
0
10 SI1 c 8 I1 e

LFSE Coulombic
t2g eg {Åo}
•
1 -2)5 0
2
•
1
A-1-*111
- 45 I1 e 0
55
3
•
1
•
1 -- 3 I1 e 0
A • 85
1
3 I1 e
•
4 11
I1 c Å o+ I1 c
m
5
A
•
4
t•
p
•
1 --
-
5 2 I1 c 4 I1 e 2Åo+ 2 I1 c
’ 11Lt
2I1 c+ 2I1 c
1
6 1
l 3 I1 c 4 I1 e 2Åo+
g5
7
A-1-ATlp
11k •
1 - 4 I1 c SI1 e Åo+ I1 c+ I1 e
8
J
l
*
•
1
•
1 - 65 SI1c 7 I1 e o
9
AT1P
J
l
*
•
1 - 35 6 I1 c 7 I1 e 0
AT-p
J O
10 l
* 7 I1 c 8I1 e O

LFSE Coulomb I1 c ßo >

d4 d5 ß o > I1c +

M 2 + (g) + 6 H 20 (l) - • [M(H20)6f+

456 11

10 - 13 2400

-2500

-2700
2+
3+
-2800
A. P. G.
Inorg. Che m. 1995 , 34 , 5666
(M 2+ Inorg. Chem -2900
1999 , 38 , 4949(M 3 + M
nU - 5 6 ny m
d
)

5200

;Et 5400

-5800

6000

6200
o 2 3 456 7 8 9 10

(b)

3+

17 L. E. Orgel, J. Chem. 50c., 1952, 4756; P. George and D S. Mc Cl ure , Prog. I norg. Chem., 1959, 1, 381
‘

18 D. A ‘ Johnson and P. G. Nelson, Inorg. Chem. , 1995, 34, 3253; 1995, 34, 5666; 1999, 38, 4949
 10- 3 457

x
x
x y
x

10 - 14 system)

nephelauxetic
O 5
d ,d ,

.6. 0 , no

10-3-5

D 4h

py U

Px, parallel set in the molecular Pz, perpendicular set in the

molecular plan e)

U
458 11:

10-8

D4h E 2C4 Cz 2Cz’ 2Cz" 254 Uh 2u v 2Ud

A 1g x2 Z2

A 2g Rz
8 1g
8 2g I
Eg 2 0 -2 0 0 2 0 -2 O O (Rx, Ry) xy
A 1u (XZ , YZ)

A 2u Z

8 1U
8 2u
Eu 2 0 -2 0 0 2 O 2 O o (x , y)

D4h E 2C4 Cz 2Cz’ 2Cz" 25 4 Uh 2u v 2Ud

4 O O 2 0 0 0 4 2 0
fll (x) 4 O 0 2 0 O O 4 -2 O
f -L(z) 4 0 0 -2 0 0 0 -4 2 o
f u = A 1g + 8 1g + Eu (U)
5, d z2 , dx2-l , Py)
[1 1 = A 2g + 8 2g + Eu (11)
dxy , (Px , Py)
r-L = A 2u + 8 2u + Eg
Pz, (dyz , dxz)

4px'

d
d x2-l' b1g , b2g )

10-8
 10- 3 459

10 - 15 D4h /' 2e ‘
(T a. Alb ‘
/ ‘
right , J. K. Burdett , M.- /

/
/

/
,-.‘“ ‘
Y Orbital Intera /
/
‘ 1 ') .... \

ctions in Chemistry,
/
/
/
‘
Interscience , New York , 1985 ,
e ao
/ “ 2u “
Px' Pv
y ‘ Pzz , /
“
/
\ //
\
\1
Y
1
/-
/ 2b ‘\ ’‘1\
\\I ‘
1\ 1 \

/
1 \
‘
‘ 1 \

h “
‘ 1“\
1
1 \
//// / 1 \ ‘
-a
/
////’/
“ ‘
\ ““
l

/ F
/ -
\ \

‘‘\ ‘ \
\

1
~// \
j
‘\ \

/ / .\ \

-‘ ?
-% eg
- j
‘ ‘\ -,
br ‘ dx
, “‘ l\l

------ \‘ \ \
l \l

‘ }
“

\\
\ \'

‘" , h
‘
/ ‘ '-- -
e
1I
,,/ //

‘
/ // “ Ig
/1

\
\
'-- - ' /

l e 1I ‘/
\

\ -'
/ /
2

la l g

dxy
Px dxz (eg ) pz
460 11:

10 - 16 D4 h z z z

y y

x
x x

ti v is tic

[Pt(CN)4f -

10-
Z2 > Ni pz

19 T. Ziegler , J. K. Nagle , J. G ‘ Snijders , and E. J. Baerends, J. Am. Cherl1. $oc. , 1989, 111 , 5631 , and th e
references ci ted therein.
20 P. Hummel, N. W. Halpern-Manners, and H. B. Gray, Inorg. Chem., 2006, 45, 7397
 10- 3 461

10-17 D4h 4 ell 11

--
3 e-- 3 V2g
b^ - /1
//1 b 211 a211 eg
s Lf g
/ 1

/
/
/
/ / l
/ / l
/ l
2 a2g
/

/
/
2b‘L U l
l

/ /
/ /
/
/
/
/
/
/
/
/
/

‘
/

. / .,I'

/ /

/. ./

/ /
/ /

/
/
•
•
_
/
7 - ...
/
•---
• / /

a
2“
\
4pz 4PX , 4py
/: \
/
-../
a
Ig \ ‘
/ /'
45 \

11

d r-
..2 - y..2

l G
l 0
6
462 11:

167H

2a2u
3

12 ,600

ß 1, ß 2'

pairing en ergy ,
b1g a21.1

10-3- 6

ß t)
ßt =

C2

dx 2 -1' dX!J' d!JZI

21 H. B. Gray and C. J. Ballhausen, J. Am. Chem . 50c., 1963, 85, 260 ‘

 10- 3 463

10-9
Td E 8C3 3C2 654 6Ud

A1 x' +I+ z2
A2
E 2 2 0 O (2x2 -x 2 -1, x' -1)
T1 3 O (Rx, Ry, Rz)
T2 3 O z) (xy, xz)

r (T 4 O O 2 A1 + T2
r 7T 8 O O O E+ T1 + T2

10-18

x
z

10-19
-•|

A
O
|•
- e

0" T,
464 11:

-
10-20 2
Ni (CO)4
c. W. Bausch liche r, D
-
Tl
P.S. I Che m. Phys., j

4s
o
- 9a ,
10 1‘ ‘~

G. Coope r, K. H
Sze , C. E. BrionOI J 4s (A ,) .//
,,"'/ 2t t LUMO)
A m. Chem. 50 c., 1989 , 117 ,
", / (e , '" (2 )
5051 450 1 (]' •• •• •• •• •• / “ / " , -/
3d(E, T2 ) “ ‘

IL/// ///
-+ 9
1'> ' --1 , ‘ //
1 •• •• /
,
2e %
••
:
y …- m
-m
-

8 C1 ,
N
•• •• •• •• •• - - - -
@
- - -
le

•• •• •• •• •• •• •• ••
7 C1 , 6 '2 40 (C1"( 2 )
Ni Ni(CO)4 4 CO

10-4
overlap 22, 23

22 E. Larsen and G. N. La Mar, J. Chem. Educ. , 1974, 51 , 633. (Note: There are misprints 011 pp. 635 and 636.)
23 J. K. Burdett, Molecular Shape5 , Wiley In terScien ce, New York , 1980
 10-4 465

10-4- 1
U dZ2

d)

10- 21
0-=----'0

-: /
d Z2\ \

N
-------‘- ---- • -- --,;‘-
é ",'"
dZ2
466 11:

10-10

,--- -------- 7
fz//3 g { t
5/ 4 j flf
r:: M :';‘ 2
A

i
LO
0 6

z2 xy xz yz
2 1.6 0 O 0 0
- 3
3 .0 2, 11, 12 2 -
4 -
4 0 0 0
1
3 1, 2 , 5 3 -
4 0 O O
-- 3
4 7.8.9.1 0 4 -
4 T
4 O O 0
1 3
4 2, 3 , 4 , 5 5 -
4 -
4 O O 0
--
5 .0= 1, 2, 6, 11 , 12 6
nU
O O 0
- 1
4 1
5 1. 2.3. 4.5 7 0 0 -3 3 -
3
1
6 1. 2. 3. 4. 5. 6 8 0 0 3
1 1
3 -
9 0 0 3
1 1
-3
10 0 0 -3
3 -9
11 -% -% 0 0
1 3
12 74 -%
O 0

[M(NH3)6]"+ U
pair)
5-31
 10-4 467

dX2

d xy d xz d yz o
' '

10-22

/:;.0 =

- - xy , xz , yz \
\

\ •• •• •• •• •• ••
•
tJ, tJ, tJ, tJ, tJ, //
468 11 :

10-9
ML4

10-4-2
CO , CN-

U eu >

dZ2

10-23

/ or d

d a •
c
 10-4 469

10-11

---;7

4-M :::2 W
--+-r-;!( fl1
5/ • M-:- ,

A di -L--• ,
6
10

z2 J? -yl xy xz yz
2 1, 6 0 O O
3 2 , 11 , 12 2 O O 0
3 1, 2, 5 3 O O O
4 7.8.9.10 4 0 0 0
4 2, 3 , 4 , 5 5 0 0 0
5 1.2.6. 11 .12 6 O O O
29 25J 2
5 1.2.3.4.5 7 -9
25J 7454 2 2§
6 1, 2 , 3 , 4 , 5, 6 8 -9
2 2;1 2 2
- )9 -
9 9 9
2 2 14
10 9
• -9 -
9
-1 -- --
3
- 74 -4 -4
11 O 4
3 1 1 1
12 0 -
4 -4 4
• -4

dxy dyv dzx

'

[M(CN)6t-
[M(CN)61n dxy
'
dyz
'

t 2g - eg
.:lo = 3eu +
470 11

10-24 l
l

-
E
= 3e +
(T {

4
7
-

- N N
“ ( - … -E -
E
1 n
- -

10-4 - 3
p, d,

10-25
//'1 ,‘
- 71
- ( _ ____ _J ‘
“

\“‘ \“••

OICJ x
d :
/ ’ Fx

10- 26
6. 0 = J {{n;r-y2
’ yz
I \
___ L G
“
“

‘ t ------- •• •• •• •• ••

2e ‘l
 471

[MX6]11-

[MX 6 t o

dXyl d y Zl

10-10
MX4

10-11

a. (T

b.

10-4-4
472 11

ethy

en> NH 3

F- > Cl - > Br- > 1

H 2o, orr,

H 20 > F- > RC0 2 - > OH - > Cl - > Br- > 1-

CO, CN- > > N0 2 - > NCS

CO, > phen > N0 2- > en > NH3 > NCS- > H 20 > F- > RC0 2- > orr > Cl- > Br- > 1
 10-4 473

10-4- 5 e u ,

2
Co +

Å Of TI o TI e
(Coulomb

~, x -- - - - - - -
2 -
10-27 [Co(H 20)6l 2+,
/
? [

[Co( H2ü)6l 3+,

-

/
/
/
/
/

AO

t t
- - -
Co 2+ [Co(H20)6l2+ -
,•• •• •• ••••••
[Co(HP)6 l3+ Co 3+

--T --
• • Z2 , X2 _ i
•
ß10 ß"
‘u

• • • • L // • •

W
•• •
i
xy , xz , yz
Fe 3+ [Fe(Hp)6 l3+ [Fe(CN)6 l3
474 11

10-12

x eu (cm- 1) ð. o =
MX 6
Cr 3+ CN 7530 -930 26 .3 10
en 7260 21 ,7 80
NH 3 7180 21 , 540
H20 7550 1850 15 ,250
F 8200 2000 16.600
CI- 5700 980 13. 180
Br 5380 950 12 , 340
4100 670 9 , 620
Ni 2+ en 4000 12, 000
NH 3 3600 10.800

B. N.

Cr3+

p- > Cl- > Br

 10-4 475

10-13 MA4B2

eu (cm- 1) eu (cm- 1)
Cr3+, 04h en 7233 0 F 7811 2016 a
7233 F 8033 2000 C

7333 CI 5558 900 a

7500 CI- 5857 1040 C

7567 Br 5341 1000 a

7500 Br 5120 750 C

6987 4292 594 b

6840 OH 8633 2151 a
7490 H20 7459 1370 a
7833 H20 7497 1410 C

7534 dmso 6769 1653 b

H20 7626 1370(assumed) 85 10 2539 a
NH 3 6967 O F 7453 175 1 a
Ni 2+, 04h
py 4670 570 CI 2980 540 C

4500 500 Br 2540 340 C

pyrazole 5480 1370 CI- 2540 380 C

5440 1350 Br 1980 240 C

[CuX 4l 2- , 02d
CI- 6764 1831 C

Br 4616 821 C

aM. Keeton, B. Fa-chun Chou, and A. B. P. Lever, Can. J. Chem. 1971, 49, 192; erratum, ibid. , 1973, 51 , 3690
bT. J. Barton and R. C. Slade, J. Chem.
50c. Oa /t on Trans ., 1975, 650
CM. Geloch and R. C. Slade, Ligand Field Parameters , Cambridge University Press, London, 1973, p. 186

24 J. K. Burdett, Molecular 5hapes , Wiley InterScience, New York, 1980, p. 157

476 11

=i 2 i:.!

Co(III)

10- 5
Jahn-Teller

Cu (11) ahn -Teller

eg Jahn-Teller

2 3 4 5 6 7 8 9 10

J-T w w S w w S

J-T w w w w S

w= 5= J-T

25 H. A. Jahn and E. Teller, ProC. R. 50c. London , 1937, A161 , 220

 10-5 Jahn-Teller 477

10-28 CP • •
Jahn-Tel ler 1/2 _y2' “““‘ t • • 1/28
1/2 .!L
e “
• 1/ 2 8 f
L-M:"-'-L
y2 L"""- L

N
•• ••
2/3 / / ddt.
1 8
l

d d T
XZ yz
dxy

10-12
ahn-Teller

Jahn-Teller Cr(III) (é), Mn (III) (d 4 ) Cu(II) (d 9 ) ,

Ni(III) (d\ Co(II)
Cr(III)
(tetragonal distortion,
d-d

Cr -Cr

Cr-Cr
Mn(III)
Cs Mn (S04h .12 H 20 [Mn (H 20)6]3+
Jahn -T eller
K2CuF 4

26 A Avdeef, J. A. Costamagna, and J. P. Fackler, Jr., Inorg. Chem., 1974, 13, 1854.
‘

27 J. P. Fackler, Jr., and A. Avdeef, Inorg. Chem. , 1974, 13, 1864

478 11:

[Cu(H 20)6f + + NH3 [Cu(NH3)(H 20)S]2+ + H 20 Kl = 20,000

[Cu(NH3)(H 20)sf + + NH3 [Cu(NH3h(H 20)4f + + H 20 K2 = 4,000

[Cu(NH3h(H 20)4f + + NH3 [Cu(NH3h (H 20 h f + + H 20 K3 = 1,000

[Cu(NH3h (H 20 h ]2+ + NH3 [Cu(NH3MH 20 h ]2+ + H 20 K4 = 200

[Cu(NH3MH20hf + + NH3 [Cu(NH 3)s(H 20)f + + H 20 Ks = 0.3

[C u(NH 3)s(H 20)f + + NH3 [C u (NH 3)6f + + H 20 K6 =

C u(II)

10- 6

d8, d9,
d8, d9,

28 R. M. Smith and A. E. Martell, Critical Stability Constants , Vol. 4, fnorganic Complexes , Plenum Press, New
York, 1976, p. 41
29 N. N. Greenwood and A. Earnshaw, the Elements , Pergamon Press, Elmsford , NY, 1984, pp
138S-1386.
 479

10-29 0

(a)
-2
(b) - --

4 ---- -

-6 -1 / ---- -- /
-' -",
-' '
/
-8 /
/

-10 / .:
/

/
-12
0 2 4 6 8 10

(a)

0
/ 1----
i I
-2 / 1---
// |

-4

)
/ ./
/

-10

- 12
0 2 4 6 8 10

(b)

dO/
480 11:

10-30 M 2 + 0
•
\

-5 ------ d10
‘
\
_._.- d5
oí
ii- - 10 -
___

• 15 s

-20 ‘
‘

-25
0 2 4 6 8 10

d5, d6,

10-

of

dO/ d5/ d 10

30 J. K. Burdett, J. Chem. $O c. Oalton Trans. , 1976, 1725.

 481

Cu(II) (d 9)

C u (II)

[Co(NH 3)6][CuCls] [CuCls]3-

d8 Au(III),
Pt(II), Pd (II) [N iCl4f- , [Ni(enhf+

d 7 Co(II) [CoC14f
[Co(H 20)6f+)
([Co(salen)], salen =

bis (sa1icylaldeh yeethylenediimine)).

10- 7 overlap)

MLs
D 3h

31 N. N . Greenwood and A. Earnshaw, Chemistry 01 the Ele l1l enls , 2nd ed. , Butterworth-Heinemann , Oxford ,
1997
482 11

D3h E 2C3 3C2 CTh 253 3 CT v

r 5 2 1 3 0 3
A 1' S

A1’ dz2
A 2" PZ
E’ 2 O 2 O Py) , (dx2 _ y , d xy)

10-13

10-31 ,:' d z2

‘ y ‘I

- - - - --;------ - - - -
d" ’

•• •• •• ••
\
•• •• •• ••
'---- -
 483

One of the best sources is G. Wilkinson , R. D. Gillard, and J. A. McCleverty , eds ., Comprehensive Coordination Chemistry ,
Pergamon Press , Elmsford , NY, 1987; Vo l. 1, Theory and Background and Vo l. 2, Ligands , are particularly usefu l. Others includ
the books cited in Chapter 4, which include chapters on coordination compounds. Some older, but still useful , sources are C.
J. Ballhausen, Intorduction to Field Theory, McGraw-Hill, New York , 1962; T. M. Dunn, D. S. McCl ure , and R. G
Pearson, Crystal Field Theory , Harper & Row, NY, 1965; and C. J. Ballhausen and H. B. Gray, Molecular Orbital Theory , W. A.
New York, 1965.
More recent volumes include T. A. Albright, J. K. Burdett, and M. Y. Whangbo, Orbital in Chemistry, Wiley-
INterscience, New York, 1985; and the related text by T. A. Albright and J. K. Burdett, Problems in Molecular Orbital Theory ,
Oxford University Press, Oxford, 1992, which offers examples of many problems , and their solutions. Discussions of angular
overlap and a variety of other aspects of orbital interactions in coordination complexes are provided in J. K. Burdett,
Shapes , John Wiley & Sons , New York, 1980, and B. N. Figgis and M. A. Hitchman, Ligand Field Theory and It s
Applications , Wiley-VCH, New York , 2000 Discussions of computational method are provided in A. Leach, Molecular
‘

nd
uU
Modeling: Principles and Applications, 2 ed ., Prentice Hall, Upper Saddle River , N J, 2001 , and C. J. Cramer, Essentials of
Computational Chemistry: Theory and Models , Wiley, Chichester, UK, 2002.

overlap model) Field ligand)

overlap method) Stabilization Energy, LFSE) bond theory)
theory) field theory) moment)
spin) series) ratio)
magneic constant) susceptibility)
moment) ligand) spin)
moment) spectrum)
lignad (M • L) bonding magnetic spin)
moment) back bonding)
to-metal (L • M) bonding constant)

10.1 10.2

b. [Co(H20)6f+ a. [M(H20)613+
c. [Co(H 20)61 3+ b. [ MBr 4r
d. d7 c. [M(CN)613
e. Bohr d. LFSE = [M(H20)6f+
484 11

10.3 K.R. Kunze , D.L. Perry, and

a. L. J. Wilson, Inorg. Che111. 1977, 16, 594).

b. LFSE = - 2.4 150

[M(H 20)6]3+
c. [M Cl4 ]

d. MC1 2 >5 .3
M-Cl

10.4 [M(en)(H 20)4f +, [M(en h( H 20hf+,

[M(enhf+ 25 0 C R S
\ \
N 4 M
/ /
R O

d9
10.10
IM (e n)(H 20)4]2+ [M (enh(H 20)2]2+ [M(en)3f+ Zn)
Cu 3 X 10 10 1 X 10 9 [M(H 20)6f + + 6 N H 3 -• [M(NH3)6]2+ + 6 H 20
Ni 2X10 7 1 X 10 6 1 X 104
10.11
A1
10.5 3.9
E+T ]
10.12

10.6

a. [Cr(H 20)6f+
b. [Cr(CN)6]4-
b.
c. [FeC14 r c.
d. [Fe(CN)6]3-
e. [Ni(H 20)6]2+
e.
f. [Cu(enh(H 20hf+
)
10.7
10.13

O
Fe(II)
1,

10.8 Co(II)
10.14
d
10.9 te)
 485

a. (T

]
b. L ' (1)
(2) c.
c.
d. d"
Jahn-Teller
10.15 10.18

10.16 CN 24,000

10.19 Cr(III)
pyramid)

L L
F- CI- H2 0 NH 3 en CN
L- __
i Lr-7 ..:l o(cm- 1) 15 , 200 13 , 200 17 ,4 00 21 , 600 21 , 900 33 , 500
L

10.20
a.
ML4

b. d10 10.21 a.

c. b.

10.17

10.22
190
191 ,
209

10.23 a.
a. u
486 11:

[Co(CO)41 - [Cr(CN)614- [Fe(H 20)613 + [Co(N0 2)61 4- a. C-o

Mn0 4 - [Cu(H 20)6f+
b. Cr-P
b.

10.29 FeH 2
c. Co(II)
Korsgen, W. Urban, J. M. Brown, J. Chem. Phys .
1999 , 110, 3861).
10.24 2+
5, p, z

a.
b

c.
b.

10 .3 0
10.25
7
d , d8 ,
d9
fp
10.26

a.
i
a.
b.
N itrogen b .Pt p,

a. NF
1. Pt

b.
2.

NF
3.
10 .3 1 [Mn 0 4f - [Mn 0 41
10.28
Leyssens,
D. Peeters , A. G. Orpen, J. N. H a rvey , New J
Chem.2005 , 29 , 1424-1430 10.32 B. Bersuk
er, N. B. Bala banov, D. Pekker, and J. E. Boggs, J. Chem.
CO CO
I /, CO I , /CO Phys. 2002, 117, 10478
OC-.Cr'- PH , OC-.Cr-NH, a. H
OC" I OC" I
CO CO
 487

b. 10.34
c.
a.
d.

b.
e.
10 .3 5
Cr(ill)
. t 2g
10.33
a.

b.