TY - JOUR
T1 - Synthesis, reactivity, and properties of N-fused porphyrin manganese(I) tricarbonyl complexes
AU - Ikeda, Shinya
AU - Toganoh, Motoki
AU - Furuta, Hiroyuki
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2011/7/4
Y1 - 2011/7/4
N2 - The reactions of N-fused tetraphenylporphyrin (NFTPP, 1a) and its 21-substituted derivatives, 21-Br-NFTPP (1b), 21-NO2-NFTPP (1c), and 21-Bz-NFTPP (1d), with Mn(CO)5Br gave the manganese(I) tricarbonyl complexes bearing N-fused tetraphenylporphyrinato ligands (2a-d), respectively, in 46-99% yields. The complexes were characterized by mass, IR, 1H and 13C NMR spectroscopy, and the final structural proof was evident from the X-ray crystallographic analysis for 2a. The crystals of 2a•CH 2Cl2 belong to the monoclinic space group P21/n (#14), with a = 15.007(2) Å, b = 12.5455(19) Å, c = 21.150(3) Å, β = 102.227(4)°, and Z = 4. The lengths (Å) of three manganese-nitrogen and three manganese-carbon bonds are inequivalent respectively [Mn-N(2), 2.007(2); Mn-N(23), 2.033(2); Mn-N(24), 1.988(3); and Mn-CO, 1.798(4), 1.804(4), 1.841(3)], reflecting the asymmetric structure of the NFp ligand. The aromatic substitution reactions of 2a, such as nitration, formylation, and chlorination, proceeded without a loss of center metal to give the corresponding 21-nitro (2c), 21-formyl (2e), and 21-chloro (2f) derivatives, regioselectively. In the electrochemical measurements of 2, one reversible oxidation and two reversible reduction waves were observed. The redox potentials of 2 indicate the narrow energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO) being consistent with the electronic absorption spectra that display the absorption edges over 1000 nm. Protonation occurred at the inner core nitrogen of 2a upon the addition of acids, which is inferred from the 1H NMR spectra as well as theoretical calculations. By a treatment with amine N-oxides, demetalation of 2 proceeded to afford the corresponding NFP free-bases (1).
AB - The reactions of N-fused tetraphenylporphyrin (NFTPP, 1a) and its 21-substituted derivatives, 21-Br-NFTPP (1b), 21-NO2-NFTPP (1c), and 21-Bz-NFTPP (1d), with Mn(CO)5Br gave the manganese(I) tricarbonyl complexes bearing N-fused tetraphenylporphyrinato ligands (2a-d), respectively, in 46-99% yields. The complexes were characterized by mass, IR, 1H and 13C NMR spectroscopy, and the final structural proof was evident from the X-ray crystallographic analysis for 2a. The crystals of 2a•CH 2Cl2 belong to the monoclinic space group P21/n (#14), with a = 15.007(2) Å, b = 12.5455(19) Å, c = 21.150(3) Å, β = 102.227(4)°, and Z = 4. The lengths (Å) of three manganese-nitrogen and three manganese-carbon bonds are inequivalent respectively [Mn-N(2), 2.007(2); Mn-N(23), 2.033(2); Mn-N(24), 1.988(3); and Mn-CO, 1.798(4), 1.804(4), 1.841(3)], reflecting the asymmetric structure of the NFp ligand. The aromatic substitution reactions of 2a, such as nitration, formylation, and chlorination, proceeded without a loss of center metal to give the corresponding 21-nitro (2c), 21-formyl (2e), and 21-chloro (2f) derivatives, regioselectively. In the electrochemical measurements of 2, one reversible oxidation and two reversible reduction waves were observed. The redox potentials of 2 indicate the narrow energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO) being consistent with the electronic absorption spectra that display the absorption edges over 1000 nm. Protonation occurred at the inner core nitrogen of 2a upon the addition of acids, which is inferred from the 1H NMR spectra as well as theoretical calculations. By a treatment with amine N-oxides, demetalation of 2 proceeded to afford the corresponding NFP free-bases (1).
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U2 - 10.1021/ic2000393
DO - 10.1021/ic2000393
M3 - Article
C2 - 21657208
AN - SCOPUS:79959697252
VL - 50
SP - 6029
EP - 6043
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 13
ER -