An Intermolecular Hydrogen Bridge between a Porphyrinoid μ‐Oxido Diiron(III) Host and a Guest Water Molecule

Cationic nickel(II), palladium(II), and copper(II) isocorrole complexes were obtained from linear tetrapyrrolic 2,2′bidipyrrin precursors by metal-templated oxidative macrocyclization reactions using silver(I) tetrafluoroborate as the oxidant in 40-69 % yield. The new compounds were characterized by optical and resonance methods. Two products from overoxidation and attack of nucleophiles were identified by means of single-crystal X-ray diffraction, elucidating possible H atom [a] .62, triclinic, space group P1 , a = 11.4751 (2) Å, b = 12.2697(2) Å, c = 15.8838(3) Å, α = 96.196(2)°, = 102.527(2)°, γ = 116.272(2)°, V = 1903.75(7) Å 3 , Z = 2, ρ calc = 1.255 g cm -3 , μ(Cu-K α ) = 1.011 mm -1 , R 1 [I > 2σ(I)] = 0.0479, wR 2 (all data) = 0.1408. Crystal Data for 15: C 46 H 52 CuN 4 , M = 724.45, triclinic, space group P1 , a = 11.1150(5) Å, b = 12.3637(7) Å, c = 16.2701(6) Å, α = 96.602(4)°, = 102.207(3)°, γ = 115.355(5)°, V = 1920.6(2) Å 3 , Z = 2, ρ calc = 1.253 g cm -3 , μ(Cu-K α ) = 1.076 mm -1 , R 1 [I > 2σ(I)] = 0.0563, wR 2 (all data) = 0.1615. Crystal Data for 30: C 92 H 100 F 12 N 8 Ni 2 Sb 2 + 3.566×(CH 2 Cl 2 ) M = 2209.55, triclinic, space group P1, a = 17.4048(8) Å, b = 17.5535(8) Å, c = 19.7399(8) Å, α = 84.942(4)°, = 68.619(4)°, γ = 60.298(4)°, V = 4846.0(4) Å 3 , Z = 2, ρ calc = 1.510 g cm -3 , μ(Cu-K α ) = 7.190 mm -1 , R 1 [I > 2σ(I)] = 0.0628, wR 2 (all data) = 0.1701. Crystal Data for 31: C 38 H 50 N 4 NiO 2 , M = 653.53, monoclinic, space group P2 1 /c, a = 13.3144(3) Å, b = 17.0511(5) Å, c = 15.0318(3) Å, = 100.396(2)°, V = 3356.58(14) Å 3 , Z = 4, ρ calc = 1.293 g cm -3 , μ(Cu-K α ) = 1.133 mm -1 , R 1 [I > 2σ(I)] = 0.0395, wR 2 (all data) = 0.1090. CCDC 1938499 (for 13), 1938498 (for 15), 1056473 (for 30), and 1938500 (for 31) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.

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Oxidative Formation and Redox Properties of 9‐Methylisocorroles

Wicht

Bahnmüller

Thüsing

et al. 2019

Eur J Inorg Chem

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Pseudohalogenido complexes of iron-2,2′-bidipyrrins

Bröring

Köhler

Pietzonka

2012

J. Porphyrins Phthalocyanines

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The chlorido iron(III) complex of octaethyl-2,2′-bidipyrrin has been transformed to a series of pseudohalide complexes by ligand exchange reactions with azide, cyanate, thiocyanate and selenocyanate anions. All new complexes show the expected N-coordination of the axial ligand to the iron(III) center. In the solid state, all four species display an intermediate spin (S = 3/2) ground state, with a gradual increase of a high spin (S = 5/2) contribution at elevated temperatures for the members with the smallest ligand field strengths, i.e. the cyanato and the azido derivatives. In solution, proton NMR, and in particular IR spectroscopic studies support the interpretation of a high-spin state at ambient temperature throughout the series. The dependency of the spin state on the crystalline or dissolved state thus resembles that found for a similar series of halide derivatives before. In dichloromethane solution, the thiocyanato and selenocyanato complexes are very sensitive to aerial oxidation, forming oxacorrole and thiacorrole complexes as the only isolated products. These complexes show a S = 3/2 spin state in the solid as well as in solution, and their structural analyses prove the expected strong π-binding of the linear pseudohalide ion to the iron(III) central metal.

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An Intermolecular Hydrogen Bridge between a Porphyrinoid μ‐Oxido Diiron(III) Host and a Guest Water Molecule

Cited by 2 publications

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Oxidative Formation and Redox Properties of 9‐Methylisocorroles

Oxidative Formation and Redox Properties of 9‐Methylisocorroles

Pseudohalogenido complexes of iron-2,2′-bidipyrrins

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