Synthesis and characterization of electron-rich phosphido-bridged clusters

The reaction of [Ru-3(CO)(12)] with [Ir((Bu2PH)-P-t)(3)Cl] (1) in refluxing toluene leads to [Ru3Ir(CO)(8)([mu (3)-H)(mu -Cl)(2)(mu -PBu2t)(2)((Bu2PH) -P-t)] (4). The molecular structure in the solid reveals 4 as species conta ining a butterfly metal framework, Electron counting exhibits 4 with 64 clu ster valence electrons as an electron-rich cluster. The reaction of [(Cu((B u2PH)-P-t)Cl](4)] (5) with [Ru-3(CO)(12)] in refluxing toluene yields as ma in product the electron-rich 50e-cluster [Ru-3(CO)(6)(mu -Cl)(3)(mu -PBu2t) ((Bu2PH)-P-t)] (6).Furthermore, thermolysis of [Ru-3(CO)(12)] With Cy2PH in toluene leads to [Rn-3(CO)(7)(mu -H)(mu -PCy2)(3)] (7). 7 reacts with carb on monoxide under pressure yielding the 52e-complex [Ru-3(CO)(9)(mu -H)(mu -PCy2)(3)] (8). The preliminary X-ray crystal structure investigation revea ls 8 as species with three metal-metal bonds and therefore as an electron-r ich cluster.