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Reactions of [Ru 3 (CO) 10 (µ-dppm)] (1) and its ortho-metalated derivative [Ru 3 (CO) 9 {µ 3 -η 3 -P(C 6 H 5 )CH 2 P(C 6 H 5 )(C 6 H 4 )}] (11) with PhEEPh (E ) Te, Se, S) have been investigated. Treatment of 1 with PhTeTePh at room temperature afforded the dinuclear compound [Ru 2 (CO) 4 (µ-TePh) 2 (µ-dppm)] (2) and the 54-electron triruthenium compounds [Ru 3 (CO) 6 (µ 3 -Te) 2 (µ-TePh) 2 (µ-dppm)] (3) and [Ru 3 (CO) 6 (µ 3 -Te)(µ-TePh) 3 (η 1 -COPh)(µ-dppm)] (4). Analogous reactions of 1 with PhEEPh (E ) Se, S) led to [Ru 2 (CO) 8) and the 54-electron triruthenium compounds (E ) Se, 6; E ) S, 9), and [Ru 3 (CO) 6 (µ 3 -E)(µ-EPh) 3 (Ph)(µ-dppm)] (E ) Se, 7; E ) S, 10). Reactions of the ortho-metalated complex 11 with PhEEPh (E ) Te, Se, S) in refluxing THF gave exclusively [Ru 3 (CO) 6 (µ-EPh) 2 {µ 3 -η 3 -P(C 6 H 5 )CH 2 P(C 6 H 5 )(C 6 H 4 )}] (E ) Te, 12; E ) Se, 13; E ) S, 14). The new compounds have been characterized by a combination of analytical and spectroscopic methods, and molecular structures of 2-4, 7, 10, and 13 have been determined by single-crystal X-ray diffraction studies. Compounds 2, 5, and 8 have the classical "sawhorse" structure with two bridging EPh (E ) Te, Se, S) moieties and one bridging dppm ligand. Compounds 3, 6, and 9 contain a Ru 3 framework with two bridging EPh (E ) Te, Se, S) groups, one bridging dppm ligand, and two capping chalcogenido ligands. Compound 4 contains an Ru 3 core with a capping tellurido ligand, three bridging TePh moieties, one bridging dppm ligand, and a terminally coordinated benzoyl group, formed from multiple fragmentation of the PhTeTePh ligand and migratory insertion of a Ph group into a CO ligand. Compounds 7 and 10 comprise a capping chalcogenido ligand, three bridging EPh (E ) Se, 7; E ) S, 10) moieties, a bridging dppm ligand, and a terminally coordinated σ-bonded phenyl group. In compounds 12-14, the coordination of ortho-metalated diphosphine ligand is the same as in 11 and both the EPh moieties bridge the same unbridged Ru-Ru edge. Compounds 3, 6, 7, and 10 exhibit restricted fluxional behavior involving the µ-EPh moieties.