Reactions of cyclopentadienyl and methylcyclopentadienyl-tetrachloroniobium with thallium(I) 1,3-propanedithiolate yield compounds [NbCp^x(1,3-S₂C₃H₆)₂] [1, Cp^x = η-C₅H₅ (Cp); 2, Cp^x = η-C₅H₄Me (Cp′)]; similar reactions of the thallium(I) derivative of 2,2′-thiodiethanethiol afford [NbCp^xCl₂{(SC₂H₄)₂S}] (3, Cp^x = Cp; 4, Cp^x = Cp′). Reaction of [NbCp′Cl₄] with thallium(I) 2,2′-oxydiethanethiolate produces both [NbCp′Cl₂{(SC₂H₄)₂O}] 5 and [NbCp′O{(SC₂H₄)₂O}] 6. Products have been characterised analytically and by NMR spectroscopy; the solid-state structures of 1, 3, 5 and 6 have been established by XRD. Compound 1 is five-coordinate, with a distorted four-legged piano-stool geometry, compound 3 is six-coordinate with tridentate thiolate and cis-equatorial Cl ligands, compound 5 is also six-coordinate but with trans-equatorial Cl ligands, and compound 6 is five-coordinate, approximating to a trigonal bipyramidal geometry with an equatorial oxo ligand. Compounds 1 and 2 are fluxional in solution due to non-rigidity of the twist conformations of the six-membered chelate rings, as shown by VT ¹H NMR spectroscopic studies with ΔG^‡ = 42.7 ± 1.4 kJ mol⁻¹ (at 231 K) and ΔG^‡ = 43.1 ± 1.3 kJ mol⁻¹ (at 233 K), respectively, for ring inversion in toluene solutions. Cyclic voltammetric studies on 1 and 2 showed two consecutive, quasi-reversible, reduction processes, attributable to the sequential formation of mono- and di-anionic derivatives; reductions of the other compounds showed less evidence for reversibility. ESR spectra of the initial products of chemical reduction of 1 and 2 in thf, using either a sodium film or cobaltocene as reductant, are typical of those from Nb(IV) species and assigned to the respective mono-anions.