BIOINORGANIC CHEMISTRY A Short Course Second Edition

446 IRON-CONTAINING PROTEINS AND ENZYMES

TABLE 7.9 Selected Bond Distances and Angles for

Fe

O

Cu

III

II

−−()

2 -- 2

Complexes

Bond ( Å ) or Angle ( ° )

CcO (PDB: 2OCC)

a

Model Compound Crystal Structure

b

DFT, Fully Optimized

c

DFT, Constrained

c,d

EXAFS Cu or

(Fe) Edge

c

O

• Binding 2 Mode

Trans

• μ - 1,2

μ –

(^1) η
: η
2
μ –
(^1) η
: η
2
μ –
(^1) η
: η
2
μ –
η
1 :
η
2
Fe – Cu
4.85
3.916
4.006
3.700
d^
3.68 (3.71)
e
O2 – O3
1.63 (O1 – O2)
a
1.460 (6)
1.423
1.446
Cu – O2
2.02 (Cu – O2)
a
1.915 (5)
1.959
1.854
1.87
Fe – O2
2.28 (Fe – O1)
a
2.031 (4)
2.072
1.900
Fe – O3
3.52 (Fe – O2)
a
1.890 (6)
1.880
1.891
(1.94)
e
Cu – O – Fe
119.6 (O2)
a , 157.6 (O1)
a
166.3 (3)
170.1
160.6
149.9
Cu – O2 – O3
93.1 (Cu – O2 – O1)
a
103.4 (4)
109.0
101.0
Fe – O3 – O2 – Cu
126.8 (Fe – O1 – O2 – Cu)
a
178.0
− 175.9
− 163.8
a Reference 137c. In PDB: 2OCC, the oxygen atom directly bonded to heme a
Fe is labeled O1 and the oxygen atom directly bonded to CuB as O2. 3
b Distances and angles for
[(
)
(
)
(
)] TMP Fe
O
Cu
MeTPA
III
II
−−
−+ 22
5
from reference 155.
c DFT = density function theory calculation for
[( )
(
)
(
)] PFe
O
Cu TMPA
III
II
−−
−+ 22
and EXAFS data for
[(
)
(
)
(
)] F TPP Fe
O
Cu TMPA
III
II
82
2
−−
−+
from reference
153. d Fe – Cu distance constrained at 3.7 Å. e EXAFS Fe edge.