Chalcogenide-capped triruthenium clusters: X-ray structures of [Ru3(CO)6(μ3-CO){P(C4H3S)3}(μ-dppm)(μ3-O)] and [(μ-H)2Ru3(CO)6{P(C4H3S)3}(μ-dppm)(μ3-S)]

Thermolysis of Ru3(CO)10(μ-dppm) and Ru3(CO)9(PRPh2)(μ-dppm) (R = Ph, H) in presence of O2: Synthesis and structure of triruthenium clusters containing a capping-oxo ligand

“…Both clusters contain a triruthenium core capped with a triply bridging oxo-ligand on one face and a triply bridging carbonyl ligand on the opposite face. They are structurally very similar to that of the related clusters Ru 3 (CO) 6 {P(C 4 H 3 S) 3 }(µ 3 -CO)(µ 3 -O)(µ-dppm) (A) [4] and Ru 3 (CO) 5 (µ 3 -CO)(µ 3 -O)(µ-dpam) 2 (B) [5] obtained from the reactions of Ru 3 (CO) 8 (µ-dppm) and Ru 3 (CO) 8 [5], but are significantly shorter than those observed in the parent clusters Spectroscopic data show that 1 retains its solid-state structure in solution but 2 exists in two isomeric forms (Chart 2). The 31 P{ 1 H} NMR spectrum of 1 displays only a singlet at δ 26.8 for the equivalent phosphorus nuclei of dppm, whilst its 1 H NMR spectrum shows a multiplet at δ 3.62 (integrating to 2H) attributed to the methylene protons together with resonance in the aromatic region for the phenyl protons of the dppm ligand.…”

“…A literature review in this field shows that at least three carbonyls have to be replaced by phosphines from Ru 3 (CO) 12 in order to make it reactive towards O 2 that leads to the formation of oxo-capped cluster [4][5][6]. In the present work, we have investigated this area further and found that bis-phosphine substituted cluster Ru 3 (CO) 10 (µ-dppm) also reacts with O 2 to afford oxo-capped cluster, but only at more drastic conditions.…”

“…It has been known for some years that zero-valent triruthenium clusters react with elemental sulfur and its heavier congeners to afford chalcogenide-capped clusters [1][2][3][4]. In 1979, Johnson and co-workers synthesized Ru 3 (CO) 9 (µ 3 -X) 2 and Ru 3 (CO) 9 (µ-H) 2 (µ 3 -X) from the reaction of Ru 3 (CO) 12 with X n (X = S, Se, Te) in presence of CO [3].…”

“…In contrast, Ru 3 (CO) 12 does not reacts with molecular oxygen (O 2 ) to afford oxo-capped clusters since the triruthenium core is not electron-rich enough to undergo oxidation. One way to increase the electron-richness of the trinuclear core is the substitution of carbonyl(s) by more electrondonating phosphines and the phosphine-substituted derivatives of Ru 3 (CO) 12 such as Ru 3 (CO) 9 {P(C 4 H 3 S) 3 }(µ-dppm), Ru 3 (CO) 8 (µ-dppm) 2 and Ru 3 (CO) 6 (µ-dppm) 3 have been found to react with O 2 which lead to the formation of oxo-capped clusters (Chart 1) [4][5][6].…”