AbstractThe monomeric rhenium(I) complex with bidentate telluroether ligand Re(CO)3Br(PhTe(CH2)3TePh) (1) was accessible via reaction of the PhTe(CH2)3TePh with Re(CO)5Br. This chelate complex crystallized in triclinic space group\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm P}\bar 1 $\end{document}witha= 9.390(5) Å,b= 10.961(3) Å,c= 11.849(4) Åa= 63.30(3)°, β = 87.49(4)° γ = 69.31(4)°, V = 1009.5(7) Å3Z = 2, R = 0.033, and Rw= 0.034. Reaction of Re(CO)5Cl with NaTePh yielded the Re(I) specics PhTeRe(CO)5(2). This complex crystallized in triclinic space group\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm P}\bar 1 $\end{document}witha= 7.085(1) Å,b= 9.203(1) Å,c= 11.341(1) Å, α = 107.24(1)°, β = 100.56(1)°, γ = 96.47(1)°, V = 683.2(2) Å3, Z = 2, R = 0.027, Rw= 0.022. Reaction of PhTeRe(CO)5and (PhSe)2in THF at 65 °C yielded a product that was confirmed crystallographically to be the known species Re2(μ‐SePh)2(CO)8(3), in which two phenylselenolate ligands bridge the two Re(I). Compound 3 crystallized in monoclinic space group P21/n witha= 7.210(2) Å,b= 18.862(6) Å,c= 9.083(3) Å, β = 107.48(3)° V = 1178.2(7) Å3, Z = 2, R = 0.046, and Rw= 0.051. Methylation of PhTeRe(CO)5with [Me3O][BF4] afforded Re(I) product [(PhTeMe)Re(CO)5][BF4] (4). This monodentate telluroether species crystallized in monoclinic space group P21/n witha= 8.405(1) Å,b= 13.438(3) Å,c= 15.560(2) Å, β = 92.59(1)° V = 1755.5(5) Å