含二齿膦配体的二羰基铁化合物的制备及光诱导释放一氧化碳性能  

Preparation of Dicarbonyl Iron Compounds with a Bidentate Phosphine and Their CO Release Behaviors upon Irradiation

作　　者：罗佳彬 郭晋忠 肖志音[2] 钟伟[2] 李雪明 刘小明 LUO Jia-Bin;GUO Jin-Zhong;XIAO Zhi-Yin;ZHONG Wei;LI Xue-Ming;LIU Xiao-Ming(College of Chemistry and Bioengineering,Guilin University of Technology,Guilin,Guangxi 541006,China;College of Biological,Chemical Sciences and Engineering,Jiaxing University,Jiaxing,Zhejiang 314001,China)

机构地区：[1]桂林理工大学化学与生物工程学院,桂林541006 [2]嘉兴学院生物与化学工程学院,嘉兴314001

出　　处：《无机化学学报》2022年第7期1241-1251,共11页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21807047,21571083);浙江省自然科学基金(No.LQ17B010004);广西科技基地和人才专项(No.桂科AD19110029)资助。

摘　　要：一氧化碳释放剂(CORM)为CO在人体的精准输送提供了便利。为提高CORM的稳定性,以[Fe(CO)_(4)I_(2)]为前驱体,通过与二齿膦配体dppe、dppp、PNP dppe=1,2-双(二苯基膦酰)乙烷,dppp=1,3-双(二苯基膦酰)丙烷,PNP=N-环己基-N-(二苯基膦酰)-1,1-二苯基膦胺(Ph_(2)PN(cyclohexyl)PPh_(2))的配位取代反应制得了二齿膦二羰基铁化合物1-3,并利用FT-IR、UV-Vis、NMR、元素分析、单晶X射线衍射(化合物2、3)进行表征。通过红外光谱法研究了化合物1-3的降解释放CO性能,以评估其作为CORM的潜能。在二甲亚砜溶剂中、黑暗条件下这些化合物表现出良好稳定性;但在可见光(红光、绿光、蓝光)照射下,均可降解释放CO,其降解速率与光源的能量和化合物的结构有关。此外,在蓝光和绿光照射下,发现化合物1和2可从顺式构型向反式构型发生转化,而红光下因能量不足未见构型转化。CO-releasing molecule(CORM) facilitates the precise delivery of CO in the human body. To improve the stability of CORM, iron dicarbonyl compounds bearing a bidentate phosphine ligand, [Fe(cis-CO)_(2)(dppe)I_(2)](1, dppe=1, 2-bis(diphenylphosphino)ethane), [Fe(cis-CO)_(2)(dppp)I_(2)](2, dppp=1, 3-bis(diphenylphosphino)propane), and[Fe(trans-CO)_(2){Ph_(2)PN(cyclohexyl)PPh_(2)}I_(2)](3) were prepared by reacting of the precursor [Fe(CO)_(4)I_(2)] with the phosphine ligands via coordination substitution reactions. The compounds were structurally characterized by means of FT-IR, UV-Vis, NMR, elemental analysis, and single-crystal X-ray diffraction(for compounds 2 and 3). Moreover,CO-releasing behaviors of compounds1-3in DMSO were investigated by FT-IR to evaluate their application as a potential CORM. As demonstrated by the FT-IR spectroscopical monitoring, these compounds exhibited good stability in the dark but were easily decomposed to release CO upon irradiation of visible lights(red, green, and blue lights).Their degradation with CO release depends on the energy of the light source and the chemical structures of the compounds. Moreover, isomerization transformations of compounds 1 and 2 from cis-to trans-dicarbonyl configuration were confirmed by the FT-IR spectroscopy under the green and blue lights. However, the red light did not trigger the configuration conversion due to its low energy. Among them, the trans-dicarbonyl compound 3 exhibited the best stability upon the irradiation, which adopted a zero-order model for the photo-induced CO release. CCDC: 2154703,2;2154704,3.

关 键 词：羰基铁化合物 二齿膦 构型转化 光诱导 一氧化碳 动力学 

分 类 号：O614.811[理学—无机化学]