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首页> 外文期刊>Chemistry: A European journal >Synthesis and self-organization of zinc β-(dialkoxyphosphoryl) porphyrins in the solid state and in solution
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Synthesis and self-organization of zinc β-(dialkoxyphosphoryl) porphyrins in the solid state and in solution

机译：固态和溶液中β-（二烷氧基磷酰基）锌卟啉的合成与自组织

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摘要

The first synthesis and self-organization of zinc β- phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn ~(II) complexes have been synthesized in good yields by using Pd-and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-β-(dialkoxyphosphoryl)porphyrins 1 Zn-3 Zn starting from the β-bromo-substituted zinc porphyrinate ZnTPPBr (TPP=tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)_2 (R=Et, iPr, nBu). The derivatives 1 Zn-3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72 % yield. The use of a Pd-catalyzed C-P bond-forming reaction was further extended to the synthesis of β-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H_2TPPBr _4 led to the formation of a mixture of the 2,12-and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H_2 and 6 H_2 in 81 % total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process.
机译：报道了固态和溶液中β-磷酸基卟啉锌的首次合成和自组织。 β-二烷氧基磷酰基-5,10,15,20-四苯基卟啉及其锌〜（II）配合物通过Pd和Cu介导的碳-磷键形成反应以高收率合成。铜介导的反应允许从β-溴取代的卟啉锌ZnTPPBr（TPP = tetraphenylporphyrin）和亚磷酸二烷基酯HP（O）（OR）_2（）制备单β-（二烷氧基磷酰基）卟啉1 Zn-3 Zn。 R = Et，iPr，nBu）。通过使用1-3当量的CuI，可以高收率获得1 Zn-3 Zn衍生物。当反应在催化量的钯络合物在甲苯中存在下进行时，以高达72％的收率获得所需的锌衍生物1 Zn。 Pd催化的C-P键形成反应的使用进一步扩展到了β-聚（二烷氧基磷酰基）卟啉的合成。涉及H_2TPPBr _4的连续还原和磷酸化的空前的一锅序列导致81％的总产率形成2,12-和2,13-双（二烷氧基）磷酰基卟啉5 H_2和6 H_2的混合物。根据X射线衍射研究，1 Zn和3 Zn是部分重叠的界面二聚体，这些二聚体是通过两个Zn中心通过属于相邻分子的两个磷酰基的配位而形成的。根据光谱数据（UV / Vis吸收和NMR光谱），单体和二聚体物质之间的平衡存在于1 Zn和3 Zn在弱极性溶剂中的溶液中。每种形式的比例取决于浓度，温度和痕量水或甲醇。这些特征表明，β-磷酰基卟啉锌可以被认为是光合作用过程中弱耦合叶绿素对的新型模型化合物。

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