We designed a novel naphthyridine-based supporting ligand involving two silyl coordinating moieties at 2,7-positions, t-BuNBSi, for the synthesis of dinuclear metal complexes. Reaction of a ligand precursor t-BuNBSi(H)(2) (1) with Ru-3(CO)(12) gave a di-mu-hydridodiruthenium(II,II) complex (t-BuNBSi) Ru-2(mu H)(2)(CO)(4) (2). Photoirradiation to 2 resulted in the formation of a diruthenium(I,I) complex (t-BuNBSi)Ru-2(CO)(6) (3). The Si-Ru-Ru-Si linkage of 2 takes a zigzag arrangement, whereas that of 3 adopts a roughly linear one.