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 (O 2 ) 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 ( 1 O 2 ) with ca. 1 eV higher energy than the ground state triplet oxygen ( 3 O 2 ) is employed, iron(IV)-oxo complexes can be synthesized using hydrogen donor substrates with much stronger C-H bonds. However, 1 O 2 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 1 O 2 , 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 1 O 2 , which is energetically more favorable by 0.98 eV, as compared with electron transfer from [Fe II (TMC)] 2+ to 3 O 2 . Electron transfer from [Fe II (TMC)] 2+ to 1 O 2 produces an iron(III)-superoxo complex, [Fe III (O 2 )(TMC)] 2+ , followed by abstracting a hydrogen atom from toluene by [Fe III (O 2 )(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 1 O 2 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.