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correlation in the H abstraction by non-heme iron(IV)–Oxo complexes: a DFT frontier orbital
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181. Kleespies ST, Oloo WN, Mukherjee A, Que Jr L (2015) CÀH bond cleavage by bioinspired
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54:5053–5064. https://doi.org/10.1021/ic502786y
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WR (2017) Transient formation and reactivity of a high-valent nickel(IV) oxido complex. J
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185. Serrano-Plana J, Oloo WN, Acosta-Rueda L, Meier KK, Verdejo B, Garcia-Espana E,
Basallote MG, Munck E, Que Jr L, Company A, Costas M (2015) Trapping a highly reactive
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186. Fan R, Serrano-Plana J, Oloo WN, Draksharapu A, Delgado-Pinar E, Company A, MartinDiaconescu V, Borrell M, Lloret-Fillol J, Garcia-Espana E, Guo Y, Bominaar EL, Que Jr L,
Costas M, Munck E (2018) Spectroscopic and DFT characterization of a highly reactive
nonheme Fe(V)-Oxo intermediate. J Am Chem Soc 140(11):3916–3928. https://doi.org/10.
1021/jacs.7b11400
187. Mondal B, Neese F, Bill E, Ye S (2018) Electronic structure contributions of non-heme
oxo-iron(V) complexes to the reactivity. J Am Chem Soc 140(30):9531–9544. https://doi.
org/10.1021/jacs.8b04275
188. Zima AM, Lyakin OY, Bryliakov KP, Talsi EP (2019) High-spin and low-spin perferryl
intermediates in Fe(PDP)-catalyzed epoxidations. ChemCatChem. https://doi.org/10.1002/
cctc.201900842
189. Luo YR (2007) Comprehensive handbook of chemical bond energies. CRC Press, Boca Raton
190. Rohde JU, In JH, Lim MH, Brennessel WW, Bukowski MR, Stubna A, Munck E, Nam W,
Que Jr L (2003) Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O
complex. Science 299(5609):1037–1039. https://doi.org/10.1126/science.299.5609.1037
191. Klein JEMN, Dereli B, Que Jr L, Cramer CJ (2016) Why metal–oxos react with
dihydroanthracene and cyclohexadiene at comparable rates, despite having different C–H
bond strengths. A computational study. Chem Commun 52:10509–10512. https://doi.org/10.
1039/c6cc05395e
192. Hammes-Schiffer S (2001) Theoretical perspectives on proton-coupled electron transfer
reactions. Acc Chem Res 34:273–281. https://doi.org/10.1021/ar9901117
193. Mayer JM (2011) Understanding hydrogen atom transfer: from bond strengths to Marcus
theory. Acc Chem Res 44:36–46. https://doi.org/10.1021/ar100093z
194. Hammes-Schiffer S (2015) Proton-coupled electron transfer: moving together and charging
forward. J Am Chem Soc 137:8860–8871. https://doi.org/10.1021/jacs.5b04087
195. Klein JEMN, Knizia G (2018) cPCET versus HAT: a direct theoretical method for
distinguishing X–H bond-activation mechanisms. Angew Chem Int Ed 57:11913–11917.
https://doi.org/10.1002/anie.201805511
196. Knizia G (2013) Intrinsic atomic orbitals: an unbiased bridge between quantum theory and
chemical concepts. J Chem Theor Comput 9:4834–4843. https://doi.org/10.1021/ct400687b
Dealing with Spin States in Computational Organometallic Catalysis
225
201200689
179. Saouma CT, Mayer JM (2014) Do spin state and spin density affect hydrogen atom transfer
reactivity? Chem Sci 5:21–31. https://doi.org/10.1039/C3SC52664J
180. Kazaryan A, Baerends EJ (2015) Ligand field effects and the high spin–high reactivity
correlation in the H abstraction by non-heme iron(IV)–Oxo complexes: a DFT frontier orbital
perspective. ACS Catal 5:1475–1488. https://doi.org/10.1021/cs501721y
181. Kleespies ST, Oloo WN, Mukherjee A, Que Jr L (2015) CÀH bond cleavage by bioinspired
nonheme oxoiron(IV) complexes, including hydroxylation of n-butane. Inorg Chem
54:5053–5064. https://doi.org/10.1021/ic502786y
182. Padamati SK, Angelone D, Draksharapu A, Primi G, Martin DJ, Tromp M, Swart M, Browne
WR (2017) Transient formation and reactivity of a high-valent nickel(IV) oxido complex. J
Am Chem Soc 139:8718–8724. https://doi.org/10.1021/jacs.7b04158
183. Unjaroen D, Swart M, Browne WR (2017) Electrochemical polymerization of iron(III)
polypyridyl complexes through C-C coupling of redox non-innocent phenolato ligands.
Inorg Chem 56:470–479. https://doi.org/10.1021/acs.inorgchem.6b02378
184. Chen J, Draksharapu A, Angelone D, Unjaroen D, Padamati SK, Hage R, Swart M, Duboc C,
Browne WR (2018) H 2 O 2 oxidation by Fe
III
-OOH intermediates and its impact on catalytic
efficiency. ACS Catal 8:9665–9674. https://doi.org/10.1021/acscatal.8b02326
185. Serrano-Plana J, Oloo WN, Acosta-Rueda L, Meier KK, Verdejo B, Garcia-Espana E,
Basallote MG, Munck E, Que Jr L, Company A, Costas M (2015) Trapping a highly reactive
nonheme iron intermediate that oxygenates strong C-H bonds with stereoretention. J Am
Chem Soc 137(50):15833–15842. https://doi.org/10.1021/jacs.5b09904
186. Fan R, Serrano-Plana J, Oloo WN, Draksharapu A, Delgado-Pinar E, Company A, MartinDiaconescu V, Borrell M, Lloret-Fillol J, Garcia-Espana E, Guo Y, Bominaar EL, Que Jr L,
Costas M, Munck E (2018) Spectroscopic and DFT characterization of a highly reactive
nonheme Fe(V)-Oxo intermediate. J Am Chem Soc 140(11):3916–3928. https://doi.org/10.
1021/jacs.7b11400
187. Mondal B, Neese F, Bill E, Ye S (2018) Electronic structure contributions of non-heme
oxo-iron(V) complexes to the reactivity. J Am Chem Soc 140(30):9531–9544. https://doi.
org/10.1021/jacs.8b04275
188. Zima AM, Lyakin OY, Bryliakov KP, Talsi EP (2019) High-spin and low-spin perferryl
intermediates in Fe(PDP)-catalyzed epoxidations. ChemCatChem. https://doi.org/10.1002/
cctc.201900842
189. Luo YR (2007) Comprehensive handbook of chemical bond energies. CRC Press, Boca Raton
190. Rohde JU, In JH, Lim MH, Brennessel WW, Bukowski MR, Stubna A, Munck E, Nam W,
Que Jr L (2003) Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O
complex. Science 299(5609):1037–1039. https://doi.org/10.1126/science.299.5609.1037
191. Klein JEMN, Dereli B, Que Jr L, Cramer CJ (2016) Why metal–oxos react with
dihydroanthracene and cyclohexadiene at comparable rates, despite having different C–H
bond strengths. A computational study. Chem Commun 52:10509–10512. https://doi.org/10.
1039/c6cc05395e
192. Hammes-Schiffer S (2001) Theoretical perspectives on proton-coupled electron transfer
reactions. Acc Chem Res 34:273–281. https://doi.org/10.1021/ar9901117
193. Mayer JM (2011) Understanding hydrogen atom transfer: from bond strengths to Marcus
theory. Acc Chem Res 44:36–46. https://doi.org/10.1021/ar100093z
194. Hammes-Schiffer S (2015) Proton-coupled electron transfer: moving together and charging
forward. J Am Chem Soc 137:8860–8871. https://doi.org/10.1021/jacs.5b04087
195. Klein JEMN, Knizia G (2018) cPCET versus HAT: a direct theoretical method for
distinguishing X–H bond-activation mechanisms. Angew Chem Int Ed 57:11913–11917.
https://doi.org/10.1002/anie.201805511
196. Knizia G (2013) Intrinsic atomic orbitals: an unbiased bridge between quantum theory and
chemical concepts. J Chem Theor Comput 9:4834–4843. https://doi.org/10.1021/ct400687b
Dealing with Spin States in Computational Organometallic Catalysis
225