Table 1. Spectroscopic properties of low-spin heme–peroxo-complexes with TMPA-derived copper chelates (br = broad; f.d. = Fermi doublet) a .
| (DCHIm)F8FeIII–O2–CuII(L), Identity of L | UV-vis (nm) | Raman 16O2 (cm–1) |
|||
| ν(O–O) | ν(Fe–O) | ν(Cu–O) | v 2;v4 | ||
| TMPA | 426, 535, 850, 950, 1020 (br) | 812 | 623 | 535 | 1572; 1364 |
| NH2TMPA | 426, 536, 790, 900 (br) | 775 | 625 | 533 | 1570; 1364 |
| (NH2)2TMPA | 425, 538, 785, 870 (br) | 760 | 614 | 506 | 1571; 1367 |
| NH2,CH3TMPA | 425, 533, 789, 897 (br) | 765 | 610 | 510 | 1571; 1367 |
| CH3TMPA | 422, 534, 855, 980 (br) | 789 (f.d.) | 612 | 525 | 1570; 1363 |
| (CH3)2TMPA | 420, 538, 845, 940 (br) | 776 | 593 | 501 | 1570; 1363 |
| PVTMPA | 429, 536, 840 (br) | 806 | 573 | 489 | 1571; 1365 |
| A2TMPA | 426, 535, 823 (br) | 802 | 580 | 484 | 1571; 1366 |
| OCH3TMPA | 424, 539, 853, 946 (br) | 805 | 575 | 483 | 1569; 1365 |
aSee the ESI for the UV-vis spectra (Fig. S5 and S6) and for the (16O2–18O2) data and raw rR spectra (Fig. S8).