μ-Nitrido Diiron Phthalocyanine and Porphyrin Complexes: Unusual Structures With Interesting Catalytic Properties

Pentagonal-bipyramidal 4d and 5d complexes with unquenched orbital angular momentum as a unique platform for advanced single-molecule magnets: current state and perspectives

“…129 However, these ligands tend to stabilize high valence states of the transition metal atoms and to form the cation-radical form of macrocyclic porphyrin and phthalocyanine ligands. 130…”

Comparative Study of the Electronic Structures of μ-Oxo, μ-Nitrido, and μ-Carbido Diiron Octapropylporphyrazine Complexes and Their Catalytic Activity in Cyclopropanation of Olefins

“…These complexes can be oxidized or reduced to attain other oxidation states . μ-Oxo diiron phthalocyanines were found to catalyze the oxidation of aromatic compounds to corresponding quinones. , In turn, μ-nitrido diiron macrocyclic complexes have emerged as effective catalysts , for the oxidation of methane, − ethane, , alkanes, , aromatic compounds, hydroacylation of olefins as well as for oxidative defluorination and dechlorination of halogenated compounds. Although the catalytic activity of μ-carbido diiron species has not been published yet, related μ-carbido diruthenium phthalocyanine catalyzed cyclopropanation of olefins and N–H bonds …”

“…Noteworthy, the catalytic properties of porphyrazine complexes including their μ-oxo, μ-nitrido, and μ-carbido dimers have been rarely investigated compared to their porphyrin , and phthalocyanine counterparts. , One representative example is the oxidation of hydrocarbons by PhIO, iodosylbenzene sulfate, and KHSO 5 catalyzed by μ-oxo diiron­(III) octakis­(perfluorophenyl)­tetraazaporphyrin …”

“…In sharp contrast, the studies of other tetrapyrrolic catalysts for the preparation of cyclopropane derivatives are scarce. Mononuclear metal phthalocyanine complexes of Cu, Fe, Mn, Ni, Co, Ag, Zn, and Ru were evaluated in the cyclopropanation of styrenes. − Binuclear single-atom bridged phthalocyanine complexes recently introduced as efficient catalysts for the oxidation and other reactions , have never been used as the catalysts for cyclopropanation except one case. μ-Carbido diruthenium phthalocyanine in combination with ethyl diazoacetate (EDA) was shown to catalyze cyclopropanation of olefins and insertion of carbene to amine N–H bonds .…”

“…27 Noteworthy, the catalytic properties of porphyrazine complexes including their μ-oxo, μ-nitrido, and μ-carbido dimers have been rarely investigated 28 compared to their porphyrin 1,2 and phthalocyanine counterparts. 11,12 One representative example is the oxidation of hydrocarbons by PhIO, iodosylbenzene sulfate, and KHSO 5 catalyzed by μ-oxo diiron(III) octakis(perfluorophenyl)tetraazaporphyrin. 29 In the present work, μ-oxo, μ-nitrido, and μ-carbido diiron octapropylporphyrazine complexes, (FePzPr 8 ) 2 X (X = O, N, C), were evaluated in the reactions of the carbene insertion to the double bond of olefins which has emerged as wellestablished synthetic approach to cyclopropyl compounds.…”