Table 3.
Selected Resonance Raman Spectroscopic Data: Heme-Peroxo-Copper Complex Core Vibrations
| system | vO–O (Δv)a | vFe–O (Δv)a | vCu–O (Δv)a | figure number, [reference] |
|---|---|---|---|---|
| tetradentate Cu ligands | ||||
| [(DCHIm)(TACNAcr)FeIII-(O22−)-CuII] + | 758 (−18) | n/r | n/r | 100933 |
| [(TPP)FeIII-(O22−)-CuII(tpa)] + | 803 (−44) | n/r | n/r | 95 A934 |
| [(TPP)FeIII-(O22−)-CuII(5-Metpa)]+ | 793 (−42) | n/r | n/r | 95 B930 |
| [(TMP)FeIII-(O22−)-CuII(5-Metpa)] + | 790 (−44) | n/r | n/r | 95C930 |
| [(TMP)FeIII-(O22−)-CuII(LOH)] + | 799 (−47) | n/r | n/r | 106 A486,935 |
| [(TMP)FeIII-(O22−)-CuII(LOMOM)] + | 801 (−46) | n/r | n/r | 935 |
| [(TMPIm)FeIII-(O22−)-CuII(LN4−OH)] + | 803/787 (−52) | n/r | n/r | 106 B485 |
| [(TMPIm)FeIII-(O2)2−-CuII(LN4−OMOM)] + | 804/752 (−52) | n/r | n/r | 935 |
| [(6L)FeIII-(O22−)-CuII]+ | 787 (−43) | 533 | n/r | 101 A936 |
| [(5L)FeIII-(O22−)-CuII]+ | 809 (−53) | n/r | n/r | 101 B936 |
| [(F8)FeIII-(O22−)-CuII(TMPA)]+ | 808 (−46) | 538 (−22) | 516 (−24) | 94498 |
| [(DCHIm)(F8)FeIII-(O22−)-CuII(TMPA)] + | 812 (−50) | 623 (−27) | 533 (−24) | 98497 |
| [(F8)FeIII-(O22−)-CuII(LN4OH)]+ | 813 (−44) | 529 (−21) | n/r | 104 B937 |
| [(F8)FeIII-(O22−)-CuII(LN4OMe)]+ | 815 (−46) | 528 (−22) | n/r | 104937 |
| [(DCHIm)(F8)FeIII-(O22−)-CuII(DCHIm)4] + | 876, 863 (−56) | 591, 585 (−27) | n/r | 108497 |
| tridentate copper ligands | ||||
| [(NMePr)FeIII(O2• −) CuI]+b | n/r | 570 (−26) | n/r | 40524 |
| [(2L)FeIII-(O2)2−-CuII]+ | 747 (−49) | n/r | n/r | 102 A938 |
| [(TMP)FeIII-(O22−)-CuII(LN3−OH)]+ | 810 (−46) | n/r | n/r | 105 A935 |
| [(TMP)FeIII-(O22−)-CuII(LN3−ONa)] + | 812 (−50) | n/r | 491(−28) | 105 B935 |
| [(F8)FeIII-(O22−)-CuII(AN)]+ | 746 (−48) | n/r | n/r | 94516 |
| [(DCHIm)(F8)FeIII-(O22−)-CuII(AN)]+ | 796 (−42) | 586 (−22) | n/r | 98928 |
| [(F8)FeIII-(O22−)-CuII(LMe2N)]+ | 752 (−43) | n/r | n/r | 103513 |
| 767 (−40) | ||||
| [(DCHIm)(F8)FeIII-(O22−)-CuII(DCHIm)3]+ | 876 (−55) | 594 (−28) | n/r | 108497 |
| [(F8)FeIII-(O22−)-CuII(MeTHF)3]+ | 737 (−41) | 555 (−27) | n/r | 107497 |
a
Values given in cm−1; values in parentheses are ∆18O2 shifts.
b
Characterized as a heme-FeIII-superoxide⋯CuI complex, see Section 2.2.2; n/r = not reported.