Intramolecular Direct Oxygen Transfer from Oxoferryl Porphyrin to a Sulfide Bond

Ueda, Takunori; Kitagishi, Hiroaki; Kawasaki, Koji

doi:10.1021/ic4026393

Cited by 17 publications

(21 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Examples of sulfur [82,102], nitrogen [103], and phosphorus [76] oxidation have also been observed. It was originally proposed that epoxidation was carried out by an Fe(IV)-oxo π* cationradical species [101].…”

Section: O-atom Transfer Reactivitymentioning

confidence: 90%

Transition Metal Complexes and the Activation of Dioxygen

Yee

Tolman

2014

Metal Ions in Life Sciences

View full text Add to dashboard Cite

In order to address how diverse metalloprotein active sites, in particular those containing iron and copper, guide O₂binding and activation processes to perform diverse functions, studies of synthetic models of the active sites have been performed. These studies have led to deep, fundamental chemical insights into how O₂coordinates to mono- and multinuclear Fe and Cu centers and is reduced to superoxo, peroxo, hydroperoxo, and, after O-O bond scission, oxo species relevant to proposed intermediates in catalysis. Recent advances in understanding the various factors that influence the course of O₂activation by Fe and Cu complexes are surveyed, with an emphasis on evaluating the structure, bonding, and reactivity of intermediates involved. The discussion is guided by an overarching mechanistic paradigm, with differences in detail due to the involvement of disparate metal ions, nuclearities, geometries, and supporting ligands providing a rich tapestry of reaction pathways by which O₂is activated at Fe and Cu sites.

show abstract

Section: O-atom Transfer Reactivitymentioning

confidence: 90%

Transition Metal Complexes and the Activation of Dioxygen

Yee

Tolman

2014

Metal Ions in Life Sciences

View full text Add to dashboard Cite

show abstract

“…Work from the same group showed that an Fe IV (O) porphyrin complexed to a per-o-methylated ß-cyclodextrin dimer was capable of a direct oxygen transfer reaction to the sulfide bond found intramolecularly on the linker. 91 …”

Section: Metal-oxo Porphyrinoid Complexes As Models For Biological Oxmentioning

confidence: 99%

Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes

2017

View full text Add to dashboard Cite

Heme proteins utilize the heme cofactor, an iron porphyrin, to perform a diverse range of reactions including dioxygen binding and transport, electron transfer, and oxidation/oxygenations. These reactions share several, key metalloporphyrin intermediates, typically derived from dioxygen and its congeners such as hydrogen peroxide, and which are comprised of metal-dioxygen, metal-superoxo, metal-peroxo, and metal-oxo adducts. A wide variety of synthetic metalloporphyrinoid complexes have been synthesized to generate and stabilize these intermediates, and then employed to determine the spectroscopic features, structures, and reactivities of such species in controlled and well-defined environments. In this review, we summarize recent findings on the reactivity of these species with common porphyrinoid scaffolds employed for biomimetic studies. The proposed mechanisms of action are emphasized. The review is organized by structural type of metal-oxygen intermediate, and broken into subsections based on the metal (manganese, iron) and porphyrinoid ligand (porphyrin, corrole, corrolazine).

show abstract

“…We previously reported the formation of a stable Cpd II‐like O=Fe IV P [P= meso ‐tetrakis(4‐sulfonatophenyl)porphyrin dianion] complex in aqueous solution containing a cyclodextrin dimer, and its intramolecular oxo‐transfer reaction (Figure ) . We utilized the supramolecular complex met‐hemoCD1 (Figure a) that was composed of meso ‐tetrakis(4‐sulfonatophenyl)porphinatoiron(III) (Fe III TPPS) and a per‐ O ‐methylated β‐cyclodextrin dimer with an ‐SCH 2 PyCH 2 S‐ (Py=pyridine‐3,5‐diyl) linker (Py3CD, Figure a) .…”

Section: Introductionmentioning

confidence: 99%

“…The reaction of met‐hemoCD1 with excess hydrogen peroxide (H 2 O 2 ) or cumene hydroperoxide (CHPO) in aqueous solution yielded the Cpd II‐like O=Fe IV P complex (abbreviated as O=Fe IV PCD1 hereafter). Owing to encapsulation by Py3CD, O=Fe IV PCD1 was so stable that it could be isolated from the excess oxidant and its derivatives by gel filtration column chromatography . The purified O=Fe IV PCD1 was spontaneously converted to its ferric (met‐hemoCD1) and ferrous‐O 2 (O 2 ‐Fe II PCD1) complexes (≈1:1 molar ratio, Figure b).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Kitagishi

Kurosawa

Kawasaki

2016

Chemistry An Asian Journal

Self Cite

View full text Add to dashboard Cite

The intramolecular oxidation of ROCH to ROCH OH, where the latter compound spontaneously decomposed to ROH and HCHO, was observed during the reaction of the supramolecular complex (met-hemoCD3) with cumene hydroperoxide in aqueous solution. Met-hemoCD3 is composed of meso-tetrakis(4-sulfonatophenyl)porphinatoiron(III) (Fe TPPS) and a per-O-methylated β-cyclodextrin dimer having an -OCH PyCH O- linker (Py=pyridine-3,5-diyl). The O=Fe TPPS complex was formed by the reaction of met-hemoCD3 with cumene hydroperoxide, and isolated by gel-filtration chromatography. Although the isolated O=Fe TPPS complex in the cyclodextrin cage was stable in aqueous solution at 25 °C, it was gradually converted to Fe TPPS (t =7.6 h). This conversion was accompanied by oxidative O-demethylation of an OCH group in the cyclodextrin dimer. The results indicated that hydrogen abstraction by O=Fe TPPS from ROCH yields HO-Fe TPPS and ROCH . This was followed by radical coupling to afford Fe TPPS and ROCH OH. The hemiacetal (ROCH OH) immediately decomposed to ROH and HCHO. This study revealed the ability of oxoferryl porphyrin to induce two-electron oxidation.

show abstract

Intramolecular Direct Oxygen Transfer from Oxoferryl Porphyrin to a Sulfide Bond

Cited by 17 publications

References 56 publications

Transition Metal Complexes and the Activation of Dioxygen

Transition Metal Complexes and the Activation of Dioxygen

Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes

Intramolecular Oxidative O‐Demethylation of an Oxoferryl Porphyrin Complexed with a Per‐O‐methylated β‐Cyclodextrin Dimer

Contact Info

Product

Resources

About