Use of Singlet Oxygen in the Generation of a Mononuclear Nonheme Iron(IV)-Oxo Complex

Nonheme iron(III)-superoxo intermediates are generated in the activation of dioxygen (O₂) by nonheme iron(II) complexes and then converted to iron(IV)-oxo species by reacting with hydrogen donor substrates with relatively weak C-H bonds. If singlet oxygen (¹O₂) with ca. 1 eV higher energy than the ground state triplet oxygen (³O₂) is employed, iron(IV)-oxo complexes can be synthesized using hydrogen donor substrates with much stronger C-H bonds. However, ¹O₂ has never been used in generating iron(IV)-oxo complexes. Herein, we report that a nonheme iron(IV)-oxo species, [Fe^IV(O)(TMC)]²⁺ (TMC = tetramethylcyclam), is generated using ¹O₂, which is produced with boron subphthalocyanine chloride (SubPc) as a photosensitizer, and hydrogen donor substrates with relatively strong C-H bonds, such as toluene (BDE = 89.5 kcal mol^-1), via electron transfer from [Fe^II(TMC)]²⁺ to ¹O₂, which is energetically more favorable by 0.98 eV, as compared with electron transfer from [Fe^II(TMC)]²⁺ to ³O₂. Electron transfer from [Fe^II(TMC)]²⁺ to ¹O₂ produces an iron(III)-superoxo complex, [Fe^III(O₂)(TMC)]²⁺, followed by abstracting a hydrogen atom from toluene by [Fe^III(O₂)(TMC)]²⁺ to form an iron(III)-hydroperoxo complex, [Fe^III(OOH)(TMC)]²⁺, that is further converted to the [Fe^IV(O)(TMC)]²⁺ species. Thus, the present study reports the first example of generating a mononuclear nonheme iron(IV)-oxo complex with the use of singlet oxygen, instead of triplet oxygen, and a hydrogen atom donor with relatively strong C-H bonds. Detailed mechanistic aspects, such as the detection of ¹O₂ emission, the quenching by [Fe^II(TMC)]²⁺, and the quantum yields, have also been discussed to provide valuable mechanistic insights into understanding nonheme iron-oxo chemistry.