First catalysis by corrole metal complexes: epoxidation, hydroxylation, and cyclopropanation

Gross, Zeev; Simkhovich, Liliya; Galili, Nitsa

doi:10.1039/a900571d

Cited by 165 publications

(98 citation statements)

References 15 publications

(9 reference statements)

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“…[21,23] In these reactions the iron complexes are actually much poorer catalysts than [Rh 2 A C H T U N G T R E N N U N G (OAc) 4 ], rhodium corroles, and ruthenium porphyrins.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Aviv

Gross

2008

Chemistry A European J

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130

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A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargyl-substituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S--H insertion) and sulfides (2,3-rearrangement reactions), which suggest similar mechanisms operate in these cases.

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“…[21,23] In these reactions the iron complexes are actually much poorer catalysts than [Rh 2 A C H T U N G T R E N N U N G (OAc) 4 ], rhodium corroles, and ruthenium porphyrins.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Aviv

Gross

2008

Chemistry A European J

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130

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“…Thus, we turned our attention to the neutral [Mn III (tpfc)] complex because deprotonated corrole, similar to porphyrinoid ligands (Scheme 1), provides four nitrogen atoms to chelate the metal ion and acts as a trianionic ligand to stabilize high oxidation states of metals. [29] Generally, corroles have a condensed tetrapyrrole ring which is more electron-rich and has a smaller cavity size compared to porphyrins. [30] 5,10,15-tris(pentafluorophenyl)corrole (H 3 tpfc; Scheme 1) bearing electron-withdrawing pentafluorophenyl groups exhibits high stability and has been widely used to stabilize high valent metal intermediates.…”

Section: Introductionmentioning

confidence: 99%

Constructing Single‐Chain Magnets by Supramolecular π–π Stacking and Spin Canting: A Case Study on Manganese(III) Corroles

Ding

Wang

et al. 2011

Chemistry A European J

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A single-chain magnet (SCM) was constructed from manganese(III) 5,10,15-tris(pentafluorophenyl)corrole complex [Mn(III) (tpfc)] through supramolecular π-π stacking without bridging ligands. In the crystal structures, [Mn(tpfc)] molecules crystallized from different solvents, such as methanol, ethyl acetate, and ethanol, exhibit different molecular orientations and intermolecular π-π interaction or weak Mn⋅⋅⋅O interaction to form a supramolecular one-dimensional motif or dimer. These three complexes show very different magnetic behaviors at low temperature. Methanol solvate 1 shows obvious frequency dependence of out-of-phase alternating-current magnetic susceptibility below 2 K and a magnetization hysteresis loop with a coercive field of 400 Oe at 0.5 K. It is the first example of spin-canted supramolecular single-chain magnet due to weak π-π stacking interaction. By fitting the susceptibility data χ(M) T (20-300 K) of 1 with the spin Hamiltonian expression H = -2J Σ(i=1)(n-1) S(Ai) S(Ai+1) + D Σ(i) S((iZ)(2)), the intrachain magnetic coupling parameter transmitted by π-π interaction of -0.31 cm(-1) and zero field splitting parameter D of -2.59 cm(-1) are obtained. Ethyl acetate solvate 2 behaves as an antiferromagnetic chain without ordering or slow magnetic relaxation down to 0.5 K. The magnetic susceptibility data χ(M) T (20-300 K) of 2 was fitted by assuming the spin Hamiltonian H = -2JΣ(i=1)(n-1) S(Ai) S(Ai+1), and the intrachain antiferromagnetic coupling constant of -0.07 cm(-1) is much weaker than that of 1. Ethanol solvate 3 with a dimer motif shows field-induced single-molecule magnet like behavior below 2.5 K. The exchange coupling constant J within the dimer propagated by π-π interaction is -0.14 cm(-1) by fitting the susceptibility data χ(M) T (20-300 K) with the spin Hamiltonian H = -2J S(A) S(B) + β(S((A)g(A)) + S((B)g(B)))H. The present studies open a new way to construct SCMs from anisotropic magnetic single-ion units through weak intermolecular interactions in the absence of bridging ligands.

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“…[6,12] The metal versus macrocycle oxidation ambiguity is particularly important in catalysis, during which the catalysts are frequently involved in redox processes. Although corrole ± metal complexes were not utilized in any catalytic application until most recently, [13] this situation is changing now as increasingly simple methods of corrole synthesis are introduced. [14] We have contributed to this field by disclosing a highly facile synthesis of tris(pentafluorophenyl)corrole [15] (H 3 (tpfc); 4 in Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Germanium, Tin, Phosphorus, Iron, and Rhodium Complexes of Tris(pentafluorophenyl)corrole, and the Utilization of the Iron and Rhodium Corroles as Cyclopropanation Catalysts

et al. 2001

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The germanium(IV), tin(IV). and phosphorus(v) complexes of tris(pentafluorophenyl)corrole were prepared and investigated by electrochemistry for elucidation of the electrochemical HOMO-LUMO gap of the corrole and the spectroscopic characteristics of the corrole pi radical cation. This information was found to be highly valuable for assigning the oxidation states in the various iron corroles that were prepared. Two iron corroles and the rhodium(I) complex of an N-substituted corrole were fully characterized by X-ray crystallography and all the transition metal corroles were examined as cyclopropanation catalysts. All iron (except the NO-ligated) and rhodium corroles are excellent catalysts for cyclopropanation of styrene, with the latter displaying superior selectivities. An investigation of the effect of the oxidation state of the metal and its ligands leads to the conclusion that for iron corroles the catalytically active form is iron(III), while all accesible oxidation states of rhodium are active.

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First catalysis by corrole metal complexes: epoxidation, hydroxylation, and cyclopropanation

Cited by 165 publications

References 15 publications

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Constructing Single‐Chain Magnets by Supramolecular π–π Stacking and Spin Canting: A Case Study on Manganese(III) Corroles

Synthesis and Characterization of Germanium, Tin, Phosphorus, Iron, and Rhodium Complexes of Tris(pentafluorophenyl)corrole, and the Utilization of the Iron and Rhodium Corroles as Cyclopropanation Catalysts

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