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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Synthesis, reactivity, and properties of N-fused porphyrin manganese(I) tricarbonyl complexes
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Synthesis, reactivity, and properties of N-fused porphyrin manganese(I) tricarbonyl complexes

机译：N-稠合卟啉锰（I）三羰基配合物的合成，反应性和性质

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The reactions of N-fused tetraphenylporphyrin (NFTPP, 1a) and its 21-substituted derivatives, 21-Br-NFTPP (1b), 21-NO_2-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 ~(13)C NMR spectroscopy, and the final structural proof was evident from the X-ray crystallographic analysis for 2a. The crystals of 2a?CH _2Cl_2 belong to the monoclinic space group P21 (#14), with a = 15.007(2) ?, b = 12.5455(19) ?, c = 21.150(3) ?, β = 102.227(4)°, and Z = 4. The lengths (?) 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).
机译：N稠合四苯基卟啉（NFTPP，1a）及其21位取代衍生物21-Br-NFTPP（1b），21-NO_2-NFTPP（1c）和21-Bz-NFTPP（1d）与Mn（ CO）_5Br分别以46-99％的收率得到了带有N-稠合四苯基卟啉配体（2a-d）的锰（I）三羰基锰配合物。通过质量，IR，〜1H和〜（13）C NMR光谱对络合物进行表征，最终结构证明从2a的X射线晶体学分析中可以看出。 2a？CH _2Cl_2的晶体属于单斜晶空间群P21 / n（＃14），其中a = 15.007（2）α，b = 12.5455（19）α，c = 21.150（3）α，β= 102.227（ [Mn-N（2），2.007（2）; 4）°，Z =4。三个锰-氮键和三个锰-碳键的长度（α）分别不等价。 Mn-N（23），2.033（2）; Mn-N（24），1.988（3）; Mn-CO，1.798（4），1.804（4），1.841（3）]，反映了NFp配体的不对称结构。进行2a的芳香取代反应（例如硝化，甲酰化和氯化），而不会损失中心金属，从而得到相应的21-硝基（2c），21-甲酰基（2e）和21-氯（2f）衍生物，区域选择性地。在2的电化学测量中，观察到一个可逆的氧化和两个可逆的还原波。氧化还原电位为2表示最高占据分子轨道和最低未占据分子轨道（HOMO-LUMO）之间的窄能隙与显示1000纳米以上吸收边的电子吸收光谱一致。加入酸后，质子化发生在2a的内核氮上，这是从〜1H NMR谱图以及理论计算得出的。通过用胺N-氧化物处理，进行2的脱金属，得到相应的NFP游离碱（1）。

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