Cymantrene–Triazole “Click” Products: Structural Characterization and Electrochemical Properties

We
report the first known examples of triazole-derivatized cymantrene
complexes (η5-[4-substituted triazol-1-yl]­cyclopentadienyl)­tricarbonylmanganese­(I),
obtained via a “click” chemical synthesis, bearing a
phenyl, 3-aminophenyl, or 4-aminophenyl moiety at the 4-position of
the triazole ring. Structural characterization data using multinuclear
NMR, UV–vis, ATR-IR, and mass spectrometric methods are provided,
as well as crystallographic data for (η5-[4-phenyltriazol-1-yl]­cyclopentadienyl)­tricarbonylmanganese­(I)
and (η5-[4-(3-aminophenyl)­triazol-1-yl]­cyclopentadienyl)­tricarbonylmanganese­(I).
Cyclic voltammetric characterization of the redox behavior of each
of the three cymantrene–triazole complexes is presented together
with digital simulations, in situ infrared spectroelectrochemistry,
and DFT calculations to extract the associated kinetic and thermodynamic
parameters. The trypanocidal activity of each cymantrene–triazole
complex is also examined, and these complexes are found to be more
active than cymantrene alone.

本研究首次报道了经“点击化学”合成的三唑修饰的环戊二烯基三羰基锰（cymantrene）配合物，即(η5-[4-取代三唑-1-基]环戊二烯基)三羰基锰(I)，该类配合物的三唑环4位带有苯基、3-氨基苯基或4-氨基苯基基团。本研究提供了采用多核核磁共振波谱、紫外-可见吸收光谱、衰减全反射红外光谱以及质谱法获得的结构表征数据，同时还给出了(η5-[4-苯基三唑-1-基]环戊二烯基)三羰基锰(I)和(η5-[4-(3-氨基苯基)三唑-1-基]环戊二烯基)三羰基锰(I)的晶体学数据。本研究对三种环戊二烯基三羰基锰-三唑配合物各自的氧化还原行为进行了循环伏安表征，并结合数字模拟、原位红外光谱电化学以及密度泛函理论（DFT）计算，提取了相关的动力学与热力学参数。此外，本研究还考察了每种环戊二烯基三羰基锰-三唑配合物的抗锥虫活性，结果发现此类配合物的活性优于单纯的环戊二烯基三羰基锰。