TY - JOUR
T1 - Activation of Dioxygen by a Mononuclear Nonheme Iron Complex
T2 - Sequential Peroxo, Oxo, and Hydroxo Intermediates
AU - Gordon, Jesse B.
AU - Vilbert, Avery C.
AU - Dimucci, Ida M.
AU - MacMillan, Samantha N.
AU - Lancaster, Kyle M.
AU - Moënne-Loccoz, Pierre
AU - Goldberg, David P.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/11/6
Y1 - 2019/11/6
N2 - The activation of dioxygen by FeII(Me3TACN)(S2SiMe2) (1) is reported. Reaction of 1 with O2 at -135 °C in 2-MeTHF generates a thiolate-ligated (peroxo)diiron complex FeIII 2(O2)(Me3TACN)2(S2SiMe2)2 (2) that was characterized by UV-vis (λmax = 300, 390, 530, 723 nm), Mössbauer (δ= 0.53, |ΔEQ| = 0.76 mm s-1), resonance Raman (RR) (ν(O-O) = 849 cm-1), and X-ray absorption (XAS) spectroscopies. Complex 2 is distinct from the outer-sphere oxidation product 1ox (UV-vis (λmax = 435, 520, 600 nm), Mössbauer (δ= 0.45, |ΔEQ| = 3.6 mm s-1), and EPR (S = 5/2, g = [6.38, 5.53, 1.99])), obtained by one-electron oxidation of 1. Cleavage of the peroxo O-O bond can be initiated either photochemically or thermally to produce a new species assigned as an FeIV(O) complex, FeIV(O)(Me3TACN)(S2SiMe2) (3), which was identified by UV-vis (λmax = 385, 460, 890 nm), Mössbauer (δ= 0.21, |ΔEQ| = 1.57 mm s-1), RR (ν(FeIV-O) = 735 cm-1), and X-ray absorption spectroscopies, as well as reactivity patterns. Reaction of 3 at low temperature with H atom donors gives a new species, FeIII(OH)(Me3TACN)(S2SiMe2) (4). Complex 4 was independently synthesized from 1 by the stoichiometric addition of a one-electron oxidant and a hydroxide source. This work provides a rare example of dioxygen activation at a mononuclear nonheme iron(II) complex that produces both FeIII-O-O-FeIII and FeIV(O) species in the same reaction with O2. It also demonstrates the feasibility of forming Fe/O2 intermediates with strongly donating sulfur ligands while avoiding immediate sulfur oxidation.
AB - The activation of dioxygen by FeII(Me3TACN)(S2SiMe2) (1) is reported. Reaction of 1 with O2 at -135 °C in 2-MeTHF generates a thiolate-ligated (peroxo)diiron complex FeIII 2(O2)(Me3TACN)2(S2SiMe2)2 (2) that was characterized by UV-vis (λmax = 300, 390, 530, 723 nm), Mössbauer (δ= 0.53, |ΔEQ| = 0.76 mm s-1), resonance Raman (RR) (ν(O-O) = 849 cm-1), and X-ray absorption (XAS) spectroscopies. Complex 2 is distinct from the outer-sphere oxidation product 1ox (UV-vis (λmax = 435, 520, 600 nm), Mössbauer (δ= 0.45, |ΔEQ| = 3.6 mm s-1), and EPR (S = 5/2, g = [6.38, 5.53, 1.99])), obtained by one-electron oxidation of 1. Cleavage of the peroxo O-O bond can be initiated either photochemically or thermally to produce a new species assigned as an FeIV(O) complex, FeIV(O)(Me3TACN)(S2SiMe2) (3), which was identified by UV-vis (λmax = 385, 460, 890 nm), Mössbauer (δ= 0.21, |ΔEQ| = 1.57 mm s-1), RR (ν(FeIV-O) = 735 cm-1), and X-ray absorption spectroscopies, as well as reactivity patterns. Reaction of 3 at low temperature with H atom donors gives a new species, FeIII(OH)(Me3TACN)(S2SiMe2) (4). Complex 4 was independently synthesized from 1 by the stoichiometric addition of a one-electron oxidant and a hydroxide source. This work provides a rare example of dioxygen activation at a mononuclear nonheme iron(II) complex that produces both FeIII-O-O-FeIII and FeIV(O) species in the same reaction with O2. It also demonstrates the feasibility of forming Fe/O2 intermediates with strongly donating sulfur ligands while avoiding immediate sulfur oxidation.
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U2 - 10.1021/jacs.9b05274
DO - 10.1021/jacs.9b05274
M3 - Article
C2 - 31647656
AN - SCOPUS:85074429366
SN - 0002-7863
VL - 141
SP - 17533
EP - 17547
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -