Fluorous triosmium clusters. Preparation, properties, and reactivity of Os3(CO)11{P(CH2CH2(CF2)5CF3)3} and Os3(CO)10{P(CH2CH2(CF2)5CF3)3}2. Crystal structure of Os3(CO)9(PPh3)2{P(CH2CH2(CF2)5CF3)3}. Ring opening metathesis polymerization of norbornene by

Several fluorous phosphine ligand triosmium carbonyl cluster derivatives, e.g., Os3(CO)11{P(CH2CH2(CF2)5CF3)3} (1) and Os3(CO)10{P(CH2CH2(CF2)5CF3)3}2 (2) have been synthesized in order to assess their properties in fluorocarbon, or fluorous, phases. Cluster 1 reacts with PPh3 above 100 °C to substitute one or two carbonyl ligands and provide the mixed ligand derivatives Os3(CO)10(PPh3){P(CH2CH2(CF2)5CF3)3}, (3) and Os3(CO)9(PPh3)2{P(CH2CH2(CF2)5CF3)3}, (4). The crystal structure of 4 has been determined by single crystal X-ray diffraction. At circa 102 °C and 1 atm H2, 1 will form the unsaturated compound (μ-H)2Os3(CO)9{P(CH2CH2(CF2)5CF3)3} (5) in modest yield. Compound 5 and the related compound (μ-H)2Os3(CO)9{P(C6H4-4-CH2CH2(CF2)7CF3)3} (6) are obtained more cleanly by treating (μ-H)2Os3(CO)10 with the corresponding fluorous phosphine ligand at room temperature followed by decarbonylation in refluxing hexane. Compounds 1–6 have been characterized by employment of IR and 1H NMR and 31P NMR spectroscopy. Partition coefficients between fluorous and non-fluorous solvents have been determined. The use of 6 as a ROMP catalyst with norbornene in a variety of organic and universal solvents is described.