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!"#$%&'()*++,-.(/(0&1%2-$3(!"#$%&!'$$()%&!""#3(4564745869(
$%&'()*+,-.(-./(0,12,-3)(*.4.52,0,&6-02%&(&.(-.728,),'8*&0&.
):;*1<%*,&(1(*=">-?&'(
@A(B(CDB(B(C(&E(!(A(DA@(
D&,&7)$(*=">-?&(
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A(DA@(!(@A(B(CDB(B(C(&E(
@H)3(I.C)-(1+$?;&%(((
J&>$1K*.(*L(,*+&1$+-%(@A(M?9(DA@(*=">-K*.(NO-;&%7?P+"Q.#R(
J&>$1K*.(*L(,*+&1$+-%(@A(M?9(DA@(*=">-K*.(NO-;&%7?P+"Q.#R(
Y244
CuB
H240
H376
H290
FeII..CuI : 5. 19 Å
S. Yoshikawa et al. Science, 1998, 280, 1723
H291
Heme a3
Metal Bridging Mechanism!for O-O Cleavage ??!
Heme a3 - CuB Active-Site!
Blomberg, Siegbahn & Wikstrom!Inorg. Chem. 2003, 42, 5231.!
Heme-Copper Oxidase Active-Site: O2-Reductive Cleavage!
Y244
CuB
H240
H376
H290
FeII..CuI : 5. 19 Å
S. Yoshikawa et al. Science, 1998, 280, 1723
H291
Heme a3
CuIN
N OH
FeIII
OO
FeIVO
CuII
OH
N NO
PMOxy
CuIIN
NOH
FeIII
O(H)O
+ (H+)
CuB
Heme a3
H376
Y244H240 H291
H290
O2
Cyt. c Oxidase Dioxygen-Reduction: O2-Intermediates
G. T. Babcock, Proc. Natl. Acad. Sci. USA 1999, 96, 12971
Fe...Cu = 4.91 Å!Fe–O = 2.52 Å!Cu–O = 2.16 Å!O–O = 1.63 Å!
For discussion of this X-ray structure, see Chem. Rev. 2004, 104, 1077-1133.
Protoctechuate 3,4-Dioxygenase!
+H2O
+
O2
- H2O+
O
OH
-OOC
OH
OH-OOC
O
OH
HO FeIII
O
NO
His
NH
O
N
NH
HO
FeIIIHis
-OOCO
O
OO
FeIII
O
HO
-OOCO
His
ON
NH
ON
NH
O
FeIIIHis
HOO
O
O
-OOC
O
OFeII-OOC
Notes: dioxygenase vs. monooxygenase; iron oxidation state does not change; iron acts as a Lewis acid; semiradical character of the catecholate ligand !activates it for direct!attack by the dioxygen molecule.!
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Note: indicating radical
mechanism here
RH = substrate
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