Facile E−E and E−C Bond Activation of PhEEPh (E = Te, Se, S) by Ruthenium Carbonyl Clusters: Formation of Di- and Triruthenium Complexes Bearing Bridging dppm and Phenylchalcogenide and Capping Chalcogenido Ligands

Reactions of [Ru3(CO)10(μ-dppm)] (1) and its ortho-metalated derivative [Ru3(CO)9{μ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}] (11) with PhEEPh (E = Te, Se, S) have been investigated. Treatment of 1 with PhTeTePh at room temperature afforded the dinuclear compound [Ru2(CO)4(μ-TePh)2(μ-dppm)] (2) and the 54-electron triruthenium compounds [Ru3(CO)6(μ3-Te)2(μ-TePh)2(μ-dppm)] (3) and [Ru3(CO)6(μ3-Te)(μ-TePh)3(η1-COPh)(μ-dppm)] (4). Analogous reactions of 1 with PhEEPh (E = Se, S) led to [Ru2(CO)4(μ-EP[Ru3(CO)6(μ3-E)2(μ-EPh)2(μ-dppm)])2(μ-dppm)] (E = Se, 5; E = S, 8) and the 54-electron triruthenium compounds (E = Se, 6; E = S, 9), and [Ru3(CO)6(μ3-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 [Ru3(CO)6(μ-EPh)2{μ3-η3-P(C6H5)CH2P(C6H5)(C6H4)}] (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 Ru3 framework with two bridging EPh (E = Te, Se, S) groups, one bridging dppm ligand, and two capping chalcogenido ligands. Compound 4 contains an Ru3 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.

本研究考察了[Ru₃(CO)₁₀(μ-双(二苯基膦)甲烷（dppm）)](1)及其邻位金属化衍生物[Ru₃(CO)₉{μ₃-η³-P(C₆H₅)CH₂P(C₆H₅)(C₆H₄)}](11)与PhEEPh（E=碲(Te)、硒(Se)、硫(S)）的反应。室温下将1与PhTeTePh反应，得到双核配合物[Ru₂(CO)₄(μ-TePh)₂(μ-dppm)](2)以及54电子三钌配合物[Ru₃(CO)₆(μ₃-Te)₂(μ-TePh)₂(μ-dppm)](3)和[Ru₃(CO)₆(μ₃-Te)(μ-TePh)₃(η¹-COPh)(μ-dppm)](4)。1与PhEEPh（E=Se、S）的类似反应则生成了[Ru₂(CO)₄(μ-EP[Ru₃(CO)₆(μ₃-E)₂(μ-EPh)₂(μ-dppm)])₂(μ-dppm)]（E=Se，5；E=S，8）以及54电子三钌配合物（E=Se，6；E=S，9）和[Ru₃(CO)₆(μ₃-E)(μ-EPh)₃(Ph)(μ-dppm)]（E=Se，7；E=S，10）。邻位金属化配合物11与PhEEPh（E=Te、Se、S）在回流四氢呋喃（THF）中反应，仅得到[Ru₃(CO)₆(μ-EPh)₂{μ₃-η³-P(C₆H₅)CH₂P(C₆H₅)(C₆H₄)}]（E=Te，12；E=Se，13；E=S，14）。所有新型配合物均通过分析与光谱联用技术进行了结构表征，其中配合物2~4、7、10及13的分子结构经单晶X射线衍射测定。配合物2、5和8均具有经典“锯架”型结构，包含两个桥联EPh（E=Te、Se、S）基团与一个桥联dppm配体。配合物3、6和9均含有三钌(Ru₃)骨架，包含两个桥联EPh（E=Te、Se、S）基团、一个桥联dppm配体与两个盖帽式硫族配体。配合物4含有三钌(Ru₃)核，包含一个盖帽式碲配体、三个桥联TePh基团、一个桥联dppm配体与一个末端配位苯甲酰基；该产物由PhTeTePh配体发生多重断裂后，苯基向羰基配体发生迁移插入反应生成。配合物7和10均包含一个盖帽式硫族配体、三个桥联EPh（E=Se，7；E=S，10）基团、一个桥联dppm配体与一个末端σ-配位苯基。在配合物12~14中，邻位金属化双膦配体的配位模式与11一致，且两个EPh基团均桥连于同一未桥联的钌-钌(Ru-Ru)键上。配合物3、6、7及10均表现出受限于μ-EPh基团的流变行为。