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48449106521
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Product Characterization Data: Cu3a: MALDI (TOF, mlz (isotope pattern, 807.2 [M, HRMS (ESI, m/z [M, Na, calcd for C50H40N4O3CuNa: 830.2294; found: 830.2267. UV-Vis (CH2Cl2):λmax, 346, 383, 432, 592, 630 nm. IR: 2961, 2924, 1734, 1599, 1539, 1489, 1441, 1384, 1344, 1319, 1225, 1153, 1086, 1073, 1029, 1009, 995, 791, 752, 700, 502 cm -1. Cu3b: MALDI (TOF, m/z (isotope pattern, 835.4 [M, HRMS (CI, m/z [M, calcd for C52H 44N4O3Cu: 835.2704; found: 835.2710. UV-Vis (CH2Cl2, λmax, 346, 383, 432, 592, 630 nm. IR: 2960, 2922, 1734, 1599, 1540, 1508, 1489, 1441, 1318, 1233, 1225, 1152, 1091, 1074, 1040, 1009, 995, 890, 833, 791, 752, 710, 700, 502 cm-1. Cu3c: MALDI (TOF, m/z (isotope pattern, 863.4 [M, HRMS ESI
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35
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48449095724
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2 (3:1).
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Isolation of Cu4b from CuOH: [2-Hydroxy-5,10,15,20- tetraphenylporphyrinato]Cu(II) (CuOH, 0.0145 mmol) was dissolved in p-dioxane (2 mL) and reacted with AgOTf(1 equiv) and n-butanol (b, 8 mL) under reflux for 20 h.
-
2O (35 mL). Extraction with EtOAc (3 x 10 mL), subsequent concentration and silica gel column chromatography purification gave Cu4b in 37% yield.
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37% yield
-
-
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40
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48449097113
-
-
2O (25 mL), and the green compound was extracted with EtOAc (3 x 10 mL). Cu1 was purified by silica gel column chromatography and isolated in 70% yield.
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2O (25 mL), and the green compound was extracted with EtOAc (3 x 10 mL). Cu1 was purified by silica gel column chromatography and isolated in 70% yield.
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41
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48449093821
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Crystals suitable for X-ray diffraction studies were obtained from slow diffusion of methanol into a CH2Cl2 solution. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication data CCDC 668819 (Cu1, and CCDC 676199 (Cu3a, CCDC 676200 (Cu3d, CCDC 676201 (H3e, Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44 (1223)336033; e-mail: deposit@ccdc.cam.ac.uk, Crystal data for Cu1: red, 0.18 x 0.18 x 0.12 mm, C44H26N4O2Cu, M, 706.23, tetragonal, a, 15.231 (5) Å, b, 15.231 (5) Å, c, 13.452 (7) Å, α, β, γ, 90°, V, 3121 (2) Å3, T, 120 (2) K, space group I42d, Z, A, ρ
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