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Parent complex (μ-PDTe)Fe2(CO)6 (1, PDTe = μ-TeCH2CH2CH2Te-μ) is prepared via a new synthetic route involving the reaction of (μ-Te2)Fe2(CO)6 with Et3BHLi, followed by treatment of (μ-LiTe)2Fe2(CO)6 with Br(CH2)3Br in a 43% yield. Further reactions of 1 with 1 equiv of monophosphines in the presence of the decarbonylating agent Me3NO afford the corresponding monophosphine-substituted complexes (μ-PDTe)Fe2(CO)5(L) (2, L = PPh3; 3, PPh2H; 4, PMe3) in 37%–47% yields, whereas the N-heterocyclic carbene IMes-monosubstituted complex (μ-PDTe)Fe2(CO)5(IMes) (5) can be prepared in a 26% yield by treatment of 1 with the in situ generated IMes from the 1,3-bis(mesityl)imidazolium salt IMes·HCl and n-BuLi. While the diphosphine-bridged single-butterfly complexes (μ-PDTe)Fe2(CO)4(dppm) (6) and (μ-PDTe)Fe2(CO)4(dppn) (7) can be prepared in 28% and 21% yields by treatment of 1 with 1 equiv of the corresponding diphosphines in refluxing xylene, treatment of 1 with 0.5 equiv of diphosphines in the presence of Me3NO results in the formation of the corresponding diphosphine-bridged double-butterfly complexes [(μ-PDTe)Fe2(CO)5]2(dppp) (8), [(μ-PDTe)Fe2(CO)5]2(dppb) (9), and [(μ-PDTe)Fe2(CO)5]2(dppf) (10) in 25–37% yields. All the new substituted model complexes 2–10 are characterized by combustion analysis and spectroscopy, and particularly for 2, 3, 5, and 7–10, by X-ray crystallography. In addition, a comparative study on the electrochemical and electrocatalytic properties of the PDTe-type model complexes 1 and 7 with their corresponding selenium and sulfur analogs are reported.
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