Reactivity of [Ru3(CO)12] towards (EPR2)(E′PR2′)NH (R = Ph, Me; R′ = Ph; E, E′ = O, S, Se): 31P and 77Se NMR spectroscopic characterization and structural analysis of the complexes formed

The reaction of [Ru3(CO)12] with the phosphorus chalcogenide ligands (EPR2)(E′PR2′)NH [E = E′ = S, R = Ph, R′ = Me (L1) and E = E′ = Se, R = R′ = Ph (L2)] produced the complexes [Ru3(μ2-H)(μ3-S){μ2-S,S,P′-(SPPh2)(PMe2)N}(CO)8] 1, [Ru3(μ2-H)(μ3-S){μ2-S,S,P′-(SPMe2)(PPh2)N}(CO)8] 2, [Ru3(μ3-S)2{μ2-P,P′-(Ph2P)(PMe2)NH}(CO)7] 3, [Ru4(μ4-S)2{μ2-P,P′-(Ph2P)(PMe2)NH}(CO)8(μ2-CO)] 4, [Ru3(μ2-H)(μ3-Se){μ2-Se,Se,P′-(SePPh2)(PPh2)N}(CO)8], 5, [Ru3(μ3-Se)2{μ2-P,P′-(PPh2)2NH}(CO)7] 6, and [Ru4(μ4-Se)2{μ2-P,P′-(PPh2)2NH}(CO)8(μ2-CO)] 7, indicating that cleavage of one of the PE bonds of the ligand is one of the first steps in the reaction, followed by the cleavage the remaining PE′ bond. The isostructural tellurium compound, [Ru4(μ4-Te)2{μ2-P,P′-(PPh2)2NH}(CO)8(μ2-CO)] 8, was also prepared through the reaction of [Ru3(CO)12] with elemental Te and (PPh2)2NH. When the monothio ligand (SPPh2)(OPPh2)NH (L3) was used, a mononuclear derivative, [Ru{(SPPh2)(OPPh2)N}2(CO)2] 9, was formed suggesting that the presence of an oxygen atom favors the breaking of the metal-metal bonds instead of that of the PO bond. All these Ru complexes were characterized by spectroscopic methods and the X-ray crystal structures of complexes 1, 2, 3, 6, 8 and 9 were determined, thus allowing comparison between similar compounds containing different donating chalcogen atoms.

Graphical abstractThe reactions of [Ru3(CO)12] with ligands of the type (EPR2)(E′PR2′)NH (E = E′ = S, R = Ph, R′ = Me and E = E′ = Se, R = R′ = Ph) yielded compounds where cleavage of the P = S and P = Se bonds occurred. When E = S, E′ = O, R = R′ = Ph, metal–metal bonds were broken to produce a mononuclear derivative with the imidophosphinate ligand. [(SPPh2)(OPPh2)N]−, coordinated to the ruthenium atom. Spectroscopic data, including 77Se NMR information, as well as the crystal structure of some of the derivatives, are reported.Figure optionsDownload full-size imageDownload as PowerPoint slide