CO and CO₂ fixation by Se-Ru-CO hydride clusters

The selective insertion of CO and CO₂ into the C-O and O-H bonds of alcohols by the Se-Ru-CO hydride clusters [(μ-H)Ru₄(CO) ₁₀Se₂]^- (1) and [(μ₃-H)Ru ₅(CO)₁₄Se]^- (2) was demonstrated by a cooperative effect of the protonic hydride, the electron-rich Ru atom, and the electronegative Se atom as well as the symmetry of the clusters. These reactions generated the first examples of Se-containing ruthenium carboxylate and alkylcarbonate clusters [{(μ-H)Ru₄(CO)₁₀Se ₂}₂{Ru₂(CO)₄(μ- η¹: η¹-OOCR)}]^3- (R = Me, 3; Et, 4) and [{(μ-H)Ru₄(CO)₁₀Se₂}₂{Ru ₂(CO)₄(μ- η¹: η¹-OOCOR)}] ^3- (R = Me, 5; Et, 6), respectively. These results disclosed herein provide a new avenue for the capture and storage of CO and CO₂ and useful synthetic routes to novel RCOO^-- and ROCOO^--bridged ruthenium selenide clusters.