Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India.
Dalton Trans. 2013 Aug 14;42(30):10798-806. doi: 10.1039/c3dt51024g. Epub 2013 Jun 18.
Synthesis and first structural characterization of hexa coordinated rhenium(I) tricarbonyl complex of 5,20-bis(p-tolyl)-10,15-bis(p-methoxyphenyl)-21-selenaporphyrin 3 are described. The Re(I) complex of 21-selenaporphyrin 3 was synthesized by treating free base 21-selenaporphyrin in 1,2-dichlorobenzene with Re(CO)5Cl at reflux for 7 h and analyzed using mass, NMR, FT-IR, UV-vis and electrochemical techniques. The first structure of metal complex of 21-selenaporphyrin was determined by X-ray single crystal analysis. The crystal structure revealed that the Re(CO)3 coordinates to two of the three inner nitrogens and one selenium to produce compound 3. The selenophene ring bent towards the Re(I) ion and the selenium is displaced by 0.41 Å from the mean plane of 24-atoms to coordinate with Re(I) ion in η(1)-fashion. The 21-selenaporphyrin is distorted in compound 3 compared to free base 21-selenaporphyrin. (1)H and (13)C NMR studies indicated that compound 3 exhibits fluxional behaviour in coordination mode of binding in solution. The compound 3 is highly stable and does not undergo decomplexation under acidic conditions. The absorption spectra showed three broad Q-bands and splitted Soret band and electrochemical studies indicated that compound 3 is stable under redox conditions.
六配位钌（I）三羰基配合物[5,20-双（对甲苯基）-10,15-双（对甲氧基苯基）-21-硒代卟啉]3 的合成及结构首次表征。通过在回流下将游离碱 21-硒代卟啉在 1,2-二氯苯中与 Re(CO)5Cl 反应 7 小时，合成了 21-硒代卟啉 3 的 Re(I)配合物，并通过质谱、NMR、FT-IR、UV-vis 和电化学技术进行了分析。金属配合物的第一个结构通过 X 射线单晶分析确定。晶体结构表明，Re(CO)3 与三个内氮中的两个和一个硒配位，生成化合物 3。硒杂环向 Re(I)离子弯曲，硒从 24 个原子的平均平面位移 0.41 Å，以η(1)-方式与 Re(I)离子配位。与游离碱 21-硒代卟啉相比，化合物 3 中的 21-硒代卟啉发生了扭曲。1H 和 13C NMR 研究表明，化合物 3 在溶液中的配位模式中表现出易变行为。该化合物 3 非常稳定，在酸性条件下不会发生去络合。吸收光谱显示三个宽 Q 带和分裂的 Soret 带，电化学研究表明化合物 3 在氧化还原条件下稳定。
