Synthesis, spectroscopic and electrochemical characterization of water soluble [(η5-C5H5)2Mo(thionucleobase/thionucleoside)]Cl2 complexes
Synthesis, spectroscopic and electrochemical characterization of water soluble [(η5-C5H5)2Mo(thionucleobase/thionucleoside)]Cl2 complexes
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DOI：
10.1016/j.ica.2003.10.026
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发表时间：
2004-03-10
影响因子：
2.8
通讯作者：
Meléndez, E
中科院分区：
文献类型：
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作者：
Chávez-Gil, TE;Meléndez, E
在THF/MeOH（2：1）混合溶剂中，将CP_2 MOCl_2（1）与相应的硫代核碱基/硫代嘌呤侧基反应，合成了一系列通式为[（mu（5）-C_5 H_5）（2）Mo（L）]Cl_2（L=6-巯基嘌呤（2），6-巯基嘌呤核糖（3），2-氨基-6-巯基嘌呤（4），2-氨基-6-巯基嘌呤核糖（5））的水溶性茂金属配合物。配合物已通过光谱方法（NMR，UV-Vis，IR和MS）进行了表征。配合物的1H-1 NMR光谱数据（DMSO-d（6））表明硫代核碱基/硫杂环丁烷侧的S-Mo-N（7）配位。在缓冲溶液中，NMR数据表明，硫代核碱基/硫代噻吩侧可能通过S（6）并通过N（7）或N（1）原子辅助而与钼保持配位。在溶液中，中间体物质如[CP 2 Mo（eta（1）-L）（H2O）]（2+/1+）（其中L充当单齿配体）是可能的。电化学表征也已通过在DMSO和缓冲溶液中的循环伏安法进行。在DMSO中，包括二氯化二茂钼在内的配合物表现出可逆的氧化还原行为。另一方面，在缓冲溶液中，氧化过程对所有物种都是不可逆的。(C)2003 Elsevier B. V.保留所有权利。
A series of water soluble molybdenocene complexes of general formula [(mu(5)-C5H5)(2)Mo(L)]Cl-2 (L=6-mercaptopurine (2), 6-mercaptopurine ribose (3), 2-amino-6-mercaptopurine (4), 2-amino-6-mercaptopurine ribose (5)) have been prepared by reacting CP2MOCl2 (1) with the corresponding thionucleobase/thionucleoside in a (2:1) THF/MeOH solvent mixture. The complexes have been characterized by spectroscopic methods (NMR, UV-Vis, IR and MS). H-1 NMR spectroscopic data (DMSO-d(6)) on the complexes suggest a S-Mo-N(7) coordination by the thionucleobase/thionucleoside. In buffer solution NMR data suggest that the thionucleobase/thionucleoside remains coordinated to molybdenum probably through S(6) and assisted by either N(7) or N(1) atoms. Intermediate species such as [CP2Mo(eta(1)-L)(H2O)](2+/1+) where the L is acting as monodentate ligand are possible in solution. Electrochemical characterization has also been pursued by cyclic voltammetry in DMSO and buffer solution. In DMSO, the complexes including the molybdenocene dichloride exhibit reversible redox behavior. On the other hand, in buffer solution, the oxidation process is irreversible for all the species. (C) 2003 Elsevier B.V. All rights reserved.