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D- .., .., .. (, ) - . . , . . THE FUNCTIONAL ROLE OF THE SYMMETRY IN THE DMETALS COORDINATION COMBINATIONS. Vasil'eva L. Yu., Lapina G. P., Vasil'eva E. Yu. (Tver, Moscow) It is discussed the functional models of the iron and manganese containing enzymes. The models are constructed on the bases of the crystalline field theory and the ligand field theory. The application of the symmetry theory makes possible to simplify the solution of SchrЖdinger equation for such systems. To construct the complexes MO and to represent the electron distribution on them. The symmetry theory makes also possible to expose the common regularities of the functional mechanism. - . : 1)
171


2. ,

; 2) - : d-, () ­ . , . , d, . Fe(II) Mn(II) , . : 1) - - ; 2) «» . () (): = c11 + c22 + ... + c n n =



n

. , , (), . Fe(II) Mn(II) ( Oh). : A (a) B ­ , E (e) ­ , T (t) ­ . g u , 1, 2 . - : - , d ­ , - 172

i =1

ci

i

, i ­ (), ci ­


.. . -- -10, 2002, .171-173

(T1u), t2g T2g T2 u . . 1. [1].
1. d d d d
6

() ­ , Oh
. ( ) (t*2g)3(t*2g)3 (t*2g)3(t*2g)2 (t*2g)3(t*2g)1 (t*2g)
3

Fe(II)

. ( ) 3 2 (t*2g) (e*g) 5 T2g (t*2g)1
4

.

-

.
1

A1g T T
2g

5

4 3

Mn(II), (t*2g)3(e*g)2 Fe(III) Mn(III), (t*2g)3(e*g)1 Fe(IV) Fe(V) (t*2g)3

A E

1g

2

5 4

g 2g

3 4

1g

A

A2g

­ 0, - - . 2 (i, i- , ) [1].
2. A1g s p T
1g 0

x y z

1/ 6 (1+2+3+4+5+6) 1/ 2 (2-6) 1/ 2 (3-6) 1/ 2 (1-4)

1/2(1x- 4x-3x +6y) 1/2(1y- 4x-2y +5x) 1/2(2x- 5y+3y +6x)

p

P E T
g

2g

d d d d

dx2dy2 1/ 2 (2+5-3-6) 1/ 12 (21+24-2-5-6-3) z2 1/2(2y+ 5x+3x +6y) xy 1/2(1x+ 4y+2x +5y) xz 1/2(1y+ 4x+3y +6x) yz

(, , ) (H2O2ё O2, , ..). - . , : Fe(II)
173


2. ,

Fe(III) . .
a1g

t1u
4p 4s 3d

t1u
a1g

e*

g

t

2g

t
a1

2g

t2
t1u
5

g

g

eg
g

eg

a1
Fe (I I I ) d

)





a1
t t
1 2

a
t

1g

t2 e
a1

t2g t2g
e
g

e

1u 2g

t1

t1u a1g
)



)

. 1. : ) ; ) , , : Fe(III) Fe(IV) Fe(V); ) Fe(III), .

.1 . H2O2, Fe(II), . Fe(III) Fe(IV) Fe(III) Fe(IV) Fe(V).

174


.. . -- -10, 2002, .171-175
t
1u

a1g
4p 4s 3d
d xy d xz d
yz

e
d z2 d


g

2

x2 y2

N( p ) z

HO 2

t

2g



t1u

eg
a1
g

N(p z ), Mn

3+

. .Mn
2+




t t
1

t
a
d
z2

1u

t
d
x2y2

1u 1g g

1g

a

a
d

d

e
x2y2

g



2

e
d
xy yz



z2

d xy d xz d

yz

t



2g

eg t1u a1

g

e e t a


dxz d

t eg t1u

2

a1
)

g

)

)



.2. - ­ : ) O
2 -

,

e



g



t



2g

; ) 2 -

O - , ; ) O 2 .

,

Mn(II) Mn(III). . [2]. , O2­, , . 175


2. ,

. . .2 - , Mn(II). , Mn(II) , 6 , . , ( Mn(III)). O 2 ( ) (3), , , e*g t*2g , . - , : 1) , d-, ; 2) ­ ; 3) , .
, 02-02-96002.



­

. 1. .. . ­ .: , 1976; 2. .., .. . ­ : , 1990.

176