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Syntheses, Structures, and Properties of Tricarbonyl (Chloro) Rhenium(I) Complexes with Redox-Active Tetrathiafulvalene−Pyrazole Ligands

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journal contribution
posted on 09.02.2009, 00:00 by Wei Liu, Jing Xiong, Yong Wang, Xin-Hui Zhou, Ru Wang, Jing-Lin Zuo, Xiao-Zeng You
A series of new tetrathiafulvalene-substituted 3,5-dimethylpyrazole ligands, 4-[{2,6,7-tris(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (MTSPz*, Pz* = 3,5-dimethylpyrazole, 4a), 4-[{6,7-benzo-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (BTSPz*, 4b), 4-[{6,7-(ethylenedithio)-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (ETSPz*, 4c) and 4-[{6,7-(propylenedithio)-2-(methylthio)-TTF-3-yl}thio]-3,5-dimethylpyrazole (PTSPz*, 4d), have been prepared by an efficient synthetic route. Further coordination reactions of the respective ligands with Re(CO)5Cl afford new rhenium(I) tricarbonyl chloro complexes, ClRe(CO)3(MTSPz*)2 (5a), ClRe(CO)3(BTSPz*)2 (5b), ClRe(CO)3(ETSPz*)2 (5c) and ClRe(CO)3(PTSPz*)2 (5d). The crystal structures of the ligand 4d and complexes 5bd have been determined by X-ray crystallography, showing nearly planar TTF units in these compounds, and the distorted octahedral geometry in all complexes. The absorption spectra and multiredox behaviors of these new compounds (4ad, 5ad) have been studied, and are rationalized based on density functional theory. The results suggest that the novel redox-active tetrathiafulvalene-pyrazole ligands are useful for the syntheses of new metal complexes.