The synthesis and characterization of a series of alkynyl half-sandwich complexes of type 2,5-((eta(5)-C5H5)(dppe)MC=C)2-(C4H2E)-C-c (E = O (11), S (12); M = Fe (a), Ru (b); dppe = 1,2-bis(diphenylphosphino)ethane) are reported. The molecular structures of 11a and 12a,b in the solid state have been determined by single-crystal X-ray diffraction. The influence of different metals and the variation of the heterocyclic bridge on the electronic interactions between the terminal redox-active units in 11a,b and 12a,b was studied using electrochemical (cyclic and square wave voltammetry) and spectroelectrochemical (in situ UV-vis/NIR, ESR, and IR spectroscopy) methods and DFT calculations. Electrochemical studies demonstrated that mixed-valent species 11a,b(+) and 12a,b(+) exhibit high thermodynamic stabilities with respect to disproportionation (K-C values from 6.87 x 10(4) to 9.33 x 10(5)). In situ spectroelectrochemical ESR and IR measurements display delocalization of the single electron between the metal centers M/M+, revealing that within this setup five-membered heterocycles are well suited to promote intramolecular metalmetal interactions. Furthermore, the UVvis/NIR spectra of mixed-valent 11a,b(+) and 12a,b(+) show intense, narrow, and nonsolvatochromic pi(d pi) -> pi*(d pi) absorptions in the NIR region with a high-energy shoulder. Both experimental and computational results suggest that at least two thermally accessible rotation conformers of the organometallic termini of 11a,b and 12a,b contribute to the electronic spectra of these compounds. One of the conformers can clearly be characterized as a delocalized class III system, while the other shows a more localized behavior.