Table 7.
Tabulated v(O–O) and v(Fe–O) Values for Ferric Heme Superoxo, Peroxo, and Hydroperoxo Entities Characterized for Enzymes and Model Systemsa
| entry no. | complex | v(O–O) (cm−1)c | v(Fe–O) (cm−1)c | ref |
|---|---|---|---|---|
| ferric heme superoxo | ||||
| (1) | Mb WT | 1103 | 578 (−29) | 1145 and 1146 |
| (2) | Mb H64L | 580 (−25) | 1147 | |
| (3) | Cyt P450 WT | 1139 (−66) | 546 (−31) | 573 |
| (4) | Cyt P450 D251N | 1136 (−66) | 537 (−30) | 574 |
| (5) | LPO pH 8.2b | 534 (−22) | 461 and 1148 | |
| (6) | LPO pH 5.6b | 558 (−24) | 1148 | |
| (7) | [(THF)(F8)FeIII-O2• −] | 1178 (−64) | 568 (−24) | 513 |
| (8) | [(PIm)FeIII-O2• −] | 1180 (−56) | 575 (–23) | 518 |
| (9) | [(6L)FeIII-O2• − FeII-Cl] | 1176 (−63) | 574 (–25) | 1149 |
| (10) | [(6L)FeIII-O2• −] | 1176 (−64) | 572 (−24) | 1149 |
| (11) | [(NMePr)FeIII–O2• −] | 575 (−21) | 524 | |
| (12) | [(NMePr)FeIII–O• −···Cu1] | 570 (−26) | 524 | |
| (13) | [(TMPImXO2EtFeIIIO• −] | 582 (−26) | 122 | |
| (14) | [(MeTHF)(F8)FeIII-O2• −] | 1175 (−63) | 574 (−24) | 497 |
| (15) | [(α4-Fe(CO2Me)4)–O2• −] | 1004 (−53) | 581 (−22) | 1237 |
| 967 (−56) | ||||
| (16) | [(α4-FeEs4)–O2• −] | 581 (−22) | 1238 | |
| (17) | [(α4-FeEs4)–O2• −] | 585 (−24) | 1238 | |
| (18) | [(FeIII(OPhP))–O2• −] | 1147 (–59) | 570 (−22) | 1239 |
| (19) | [(FeIII(HOPhP))–O2• −] | 584 (−27) | 1239 | |
| (20) | [Fe(PIM)–O2• −] | 578 (−26) | 1239 | |
| (21) | [(TMP)FeIII(O2• −)···CuI(LN3-OH)] | 576 (−26) | 935 | |
| ferric heme end-on peroxo | ||||
| (22) | Cyt P450 D251N | 792 (−38) | 553 (−27) | 574 |
| (23) | LPO pH 8.2b | 570 (−22) | 1148 | |
| (24) | [(TMPImXO2Et)FeIII-O22−] | 808 (−37) | 585 (–25) | 122 |
| ferric heme hydroperoxo | ||||
| (25) | Mb WT | 617 (−15) | 1146 | |
| (26) | Cyt P450 WT | 799 (−40) | 559 (−27) | 573 |
| (27) | Cyt P450 D251N | 774 (−37) | 564 (−28) | 574 |
| (28) | LPO pH 5.6b | 604 (−24) | 1148 | |
| (29) | [(TMPIm)FeIII-OOH] | 810 (–47) | 570 (−26) | 490 |
| (30) | [(TMPImXO2Et)FeIII-OOH] | 807 (−31) | 575 (–25) | 122 |
| (31) | [(TMPImAOH)FeIII-OOH] | 807 (−40) | 579 (−28) | 568 |
| (32) | [(TMPImAOEt)FeIII-OOH] | 811 | 576 | 568 |
| (33) | [(α4-FeEs4)-OOH] | 830 (−47) | 631 (–37) | 1052 |
a
Additional entries for biological and synthetic oxy-heme FeIII-superoxo complexes are available in the review by Momenteau and Reed.79
b
Lactoperoxidase.
c
Values in parentheses are Δ18O2 shifts.