University of Groningen
Biomimetic metal-mediated reactivity
Wegeberg, Christina
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Publication date:
2019
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Wegeberg, C. (2019). Biomimetic metal-mediated reactivity. University of Groningen.
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Appendix A
176
Appendix A
Overview of detected Fe-tpena speies and their interconvention (as of May 2014).
Appendix B
177
Appendix B
Overview of detected Fe-tpena speies and their interconvention (as of September 2018).
Appendix C
178
Appendix C
Overview of spectroscopic parameters for key iron species obtained in relation to this PhD
project
Species Oxidant Solvent max
[nm] Raman shift [cm-1] g-valuesa
δ [mm s-1]
ΔEQ
[mm s-1] Paper
[FeIII
2O(tpenaH)2](ClO4)4 n/a Solid 830 silent 0.43 1.63 I, IV
fac-[Fe(tpena)]2+ n/a MeCN
360 b 2.74, 2.29, 1.68 0.16 2.17 I, VI
mer-[Fe(tpena)]2+ n/a MeCN 4.20 0.31 n/a I, VI
[FeCl(tpenaH)]2+ n/a MeCN 312, 361 0.46 n/a IV
[FeII
(tpena)]2+
- CO2 n/a MeCN 384 654, 840, 1061 silent 0.45 n/a VI
[FeII(SBPy3)(MeCN)]2+ n/a MeCN 382, 555 628, 1158, 1551 silent 0.34 0.67 VI
[Fe(OIPh)(tpena)]2+ PhIO MeCN 428 4.50 0.44 1.71 I, II
fac-[Fe(tpenO)]2+ n/a MeOH
393 2.33, 2.15, 1.93 VII
mer-[Fe(tpenO)]2+ n/a MeOH 2.40, 2.17, 2.00 VII
Iron(III)peroxo Species [FeIII(OOH)(tpenaH)]2+ H
2O2 MeCN 520 613, 788 2.21, 2.15, 1.96 0.21 2.08 IV
[FeIII(OOH)(HtpenO)]2+ H
2O2 MeOH 537 619, 800 2.21, 2.14, 1.97 VII
2.25, 2.15, 2.00 [FeIII(OO)(tpenaH)]+ H
2O2 MeCN 675 473,815 8.8, 5.0, 4.3, 4.2, 3.5 0.48 1.21 IV
[FeIII (OO)(HtpenO)]2+ H
2O2 MeOH 716 472, 818 8.0, 4.3 VII
[FeIII(OOtBu)(tpenaH)]2+ tBuOOH MeCN 558 675, 786 2.20, 2.12, 1.97 V
[FeIII(OOcumyl)(tpenaH)]2+ cumylOOH MeCN 531 684, 782 2.19, 2.12, 1.97 V
Iron(IV)oxo Species
[FeIV=O(tpenaH)]2+ cumylOOH MeCN 730 864 V
[FeIV=O(tpenaH)]2+ tBuOOH MeCN 730 865 V
[FeIV=O(tpenaH)]2+ m-CPBA MeCN 730 c V
[FeIV=O(tpen)]2+ m-CPBA MeCN 730 833 VIII
[FeIV=O(Metpen)]2+ m-CPBA MeCN 732 832 VIII
[FeIV=O(Ettpen)]2+ m-CPBA MeCN 739 834 VIII
[FeIV=O(tpenOH)]2+ m-CPBA MeCN 732 832 VIII
[FeIV=O(Bztpen)]2+ m-CPBA MeCN 740 826 VIII
[FeIV=O(tpenaH)]2+ CAN H
2O 730 832 0.00 0.90 VIII [FeIV =18 O(tpenaH)]2+ CAN 18 O-H2O 730 796 VIII
[FeIV=O(Ettpen)]2+ CAN H
2O 718 833 VIII
[FeIV=18O(Ettpen)]2+ CAN 18O-H
2O 718 796 VIII
[FeIV=O(Bztpen)]2+ CAN H
2O 722 832 VIII
[FeIV=O(Metpen)]2+ CAN H
2O 714 832 VIII
[FeIV
=O(tpen)]2+
CAN H2O 712 833 VIII
[FeIV=O(tpen)]2+ NaOCl H
2O 712 832 VIII
[FeIV=O(Metpen)]2+ NaOCl H
2O 714 833 VIII
[FeIV=O(Ettpen)]2+ NaOCl H
2O 718 832 VIII
[FeIV=O(tpenaH)]2+ NaOCl H
2O 730 830 VIII
[FeIV
=O(Bztpen)]2+
NaOCl H2O 722 830 VIII
[FeIV=O(tpenOH)]2+ NaOCl H
2O 723 c VIII
[FeIV=O(Ettpen)]2+ NaOCl MeOH 737 832 VIII
[FeIV=O(Metpen)]2+ NaOCl MeOH 756 832 VIII
[FeIV=O(Bztpen)]2+ NaOCl MeOH 740 830 VIII
[FeIV
=O(tpenOH)]2+
NaOCl MeOH 740 831 VIII
n/a: not applicable. a geff is denoted for S = 5/
2, b photo-sensitive, ctoo short-lived for characterization with rRaman.
