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)­Ru5(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)10Se2}2{Ru2(CO)4(μ-η1:η1-OOCR)}]3– (R = Me, 3; Et, 4) and [{(μ-H)­Ru4(CO)10Se2}2{Ru2(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.