109786-99-4Relevant academic research and scientific papers
Insertion of manganese and cobalt into octaethylporphyrin N-oxide. Formation of layered diporphyrin structures joined through M-O-N links
Arasasingham, Ramesh D.,Balch, Alan L.,Olmstead, Marilyn M.,Renner, Mark W.
, p. 3562 - 3568 (2008/10/08)
Treatment of octaethylporphyrin N-oxide (OEPH2-N-O) with manganese(II) acetate or cobalt(II) acetate in ammoniacal methanol produces the cations [(OEP)MIII(OEPH2-N-O)]+ (OEP is octaethylporphyrin dianion), which have been isolated as the acetate, chloride, or hexafluorophosphate salts. [(OEP)MnIII(OEPH2-N-O)]CH3COO·3CH 2Cl2 crystallizes in the triclinic space group P1 (No. 2) with a = 10.224 (2) A?, b = 12.329 (2) A?, c = 15.021 (2) A?, α = 77.18 (2)°, β = 86.88 (2)°, γ = 82.45 (2)°, and Z = 1 at 130 K. The structure was refined to R = 0.087 for 446 parameters and 4764 reflections. [(OEP)CoIII(NH3)-(OEPH2-N-O)][CoCl 4]0.5·1.5CH2Cl2 crystallizes in the monoclinic space group P21/c (No. 14) with a = 18.566 (9) A?, b = 14.405 (9) A?, c = 28.688 (16) A?, β= 105.31 (2)°, and Z = 4, at 130 K. The structure was refined to R = 0.106 with 505 parameters and 4818 reflections. Both cations consist of a metal bound to a normal octaethylporphyrin with a monodentate O-bound OEPH2-N-O as an axial ligand. The Mn(III) complex is five-coordinate (Mn-N = 1.977-2.125 A?, Mn-O = 2.070 A? with Mn 0.148 A? out of plane) while the Co(III) complex is six-coordinate with an axial ammonia ligand (Co-Npor = 1.971-1.993 A?, Co-NH3 = 1.961 A?, Co-O = 1.976 A? with Co 0.035 A? out of plane toward O). Spectroscopic data (UV/vis, 1H NMR, and mass spectra) that confirm the structures are reported. The Mn(III) complex is high spin with μ = 4.70 μB at 296 K.
