Dimers of [Ru-2(Xap)(4)] bridged by 1,3,5-hexatriyn-diyl (Xap are 2-anilinopyridinate and its aniline substituted derivatives), [Ru-2(Xap)(4)](2)(mu-C-6) (1), were prepared. Compounds 1 reacted with 1 equiv of tetracyanoethene (TCNE) to yield the cyclo-addition/insertion products [Ru-2(Xap)(4)](2)-{mu-C CC(C(CN)(2))-C(C(CN)(2))C C} (2) and 1 equiv of Co-2(dppm)(CO)(6) to yield the eta(2)-Co-2 adducts to the middle C C bond, [Ru-2(Xap)(4)](2)(mu-C-6)(Co-2(dppm)(CO)(4)) (3). Voltammetric and spectroelectrochemical studies revealed that (i) two Ru-2 termini in 1 are sufficiently coupled with the monoanion (1(-)) as a Robin-Day class II/III mixed valence species; (ii) the coupling between two Ru-2 is still significant but somewhat weakened in 3; and (iii) the coupling between two Ru-2 is completely removed by the insertion of TCNE in 2. The attenuation of electronic couplings in 2 and 3 was further explored with both the X-ray diffraction study of representative compounds and spin-unrestricted DFT calculations.