Nickel, palladium, and copper complexes of the tripyrrolic ligand hexaethyltripyrrindione (H 3 Et 6 tpd, 1) have been prepared and characterized by UV/Vis and EPR spectroscopy, as well as by single-crystal X-ray structure determination. In all cases the metal ion is coordinated in a distorted square-planar geometry carrying a water ligand at the fourth coordination site. The Et 6 tpd ligand acts as a radical dianion in all cases. In solution, monomeric species are present in which the open-
Nickel(II) complexes of ring-contracted 9-methylisocorroles were prepared by templated macrocyclisation and act as the first porphyrinoid catalysts for C–C cross-coupling.
10-Heterocorrole complexes with oxygen, sulfur, and selenium at position 10 of the macrocycle and with the divalent ions of nickel, copper, and palladium were prepared and investigated. The focus was set on the size adaptation and matching mechanisms of cavity size versus ionic radius in corrole-type macrocycles. A full set of single-crystal X-ray analytical data revealed that in all but one case the N binding site of the ring-contracted tetrapyrrole was larger than necessary to bind the metal ion without deformation. In-plane size adaptation through M-N bond-length elongation by 2.5-3.2 % was effective, as well as pronounced out-of-plane ruffling of the macrocycle for those compounds with a more severe size mismatch. Such ruffling had been excluded for corroles previously, but is apparently the most efficient mechanism to adapt to small central ions.
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.
10‐Heterocorrole complexes with oxygen, sulfur, and selenium at position 10 of the macrocycle and with the divalent ions of nickel, copper, and palladium were prepared and investigated. The focus was set on the size adaptation and matching mechanisms of cavity size versus ionic radius in corrole‐type macrocycles. A full set of single‐crystal X‐ray analytical data revealed that in all but one case the N4 binding site of the ring‐contracted tetrapyrrole was larger than necessary to bind the metal ion without deformation. In‐plane size adaptation through M−N bond‐length elongation by 2.5–3.2 % was effective, as well as pronounced out‐of‐plane ruffling of the macrocycle for those compounds with a more severe size mismatch. Such ruffling had been excluded for corroles previously, but is apparently the most efficient mechanism to adapt to small central ions.
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