New Single-Site Palladium Catalysts for the Nonalternating Copolymerization of Ethylene and Carbon Monoxide

The synthesis and first examples of structurally characterized, single-site palladium complexes containing a phosphine sulfonate chelate (PSO) for the nonalternating copolymerization of ethylene and carbon monoxide are reported. Extra incorporation of ethylene up to 30% has been achieved relative to the alternating polyketone structure with modest activities. As exemplarily shown, high molecular weight random copolymers have been produced with Mw ≈ 370 000, polydispersity (Mw/Mn) = 2, and melting points of 220−230 °C

New Single-Site Palladium Catalysts for the Nonalternating Copolymerization of Ethylene and Carbon Monoxide

The synthesis and first examples of structurally characterized, single-site palladium complexes containing a phosphine sulfonate chelate (PSO) for the nonalternating copolymerization of ethylene and carbon monoxide are reported. Extra incorporation of ethylene up to 30% has been achieved relative to the alternating polyketone structure with modest activities. As exemplarily shown, high molecular weight random copolymers have been produced with Mw ≈ 370 000, polydispersity (Mw/Mn) = 2, and melting points of 220−230 °C

New Single-Site Palladium Catalysts for the Nonalternating Copolymerization of Ethylene and Carbon Monoxide

The synthesis and first examples of structurally characterized, single-site palladium complexes containing a phosphine sulfonate chelate (PSO) for the nonalternating copolymerization of ethylene and carbon monoxide are reported. Extra incorporation of ethylene up to 30% has been achieved relative to the alternating polyketone structure with modest activities. As exemplarily shown, high molecular weight random copolymers have been produced with Mw ≈ 370 000, polydispersity (Mw/Mn) = 2, and melting points of 220−230 °C

New Single-Site Palladium Catalysts for the Nonalternating Copolymerization of Ethylene and Carbon Monoxide

The synthesis and first examples of structurally characterized, single-site palladium complexes containing a phosphine sulfonate chelate (PSO) for the nonalternating copolymerization of ethylene and carbon monoxide are reported. Extra incorporation of ethylene up to 30% has been achieved relative to the alternating polyketone structure with modest activities. As exemplarily shown, high molecular weight random copolymers have been produced with Mw ≈ 370 000, polydispersity (Mw/Mn) = 2, and melting points of 220−230 °C

Mass Spectrometric Method for the Rapid Characterization of Transition Metal Carbonyl Cluster Reaction Mixtures

Energy-dependent electrospray ionization mass spectrometry (EDESI-MS) has been applied to the characterization of reaction products that contain a mixture of metal carbonyl cluster anions. The technique allows rapid identification of the components and provides molecular weight (parent ion), ion composition (isotope pattern), and structural information (fragmentation pattern). The spectra are presented as a two-dimensional map of cone voltage versus mass-to-charge ratio which resolves each component of the reaction product. The EDESI-MS technique is illustrated using the reaction products obtained from the reaction of [Ru6C(CO)17] and [PPN][M(CO)4] where M = Co or Ir. The anions identified from these reactions are [Ru5CoC(CO)16]-, [Ru3Co(CO)13]-, [RuCo3(CO)12]-, [HRu4Co2C(CO)15]-, [Ru5IrC(CO)16]-, [Ru3Ir(CO)13]-, and [RuIr3(CO)12]-. All the compounds have been fully characterized as their [PPN]+ salts by EDESI-MS together with other methods including single-crystal X-ray diffraction for [PPN][Ru5CoC(CO)16]

Analysis of Low Oxidation State Transition Metal Clusters by Laser Desorption/Ionization Time-of-Flight Mass Spectrometry

A variety of homonuclear and heteronuclear transition metal carbonyl clusters have been analyzed by ultraviolet laser desorption/ionization time-of-flight mass spectrometry. The spectra were recorded in negative and positive ion modes, using both linear and reflective techniques. A range of different clusters based on different nuclearities, geometries, and ligand types, which include hydrides, phosphines, nitriles, and cyclopentadienyl ligands and naked main group atoms, were studied. These experiments have allowed us to construct a detailed picture of the technique for the analysis of transition metal carbonyl clusters and their derivatives. In general, extensive reactions are observed, cluster aggregation reactions in particular, and from a comparison of the spectra obtained, some mechanistic inferences concerning the aggregation processes have been drawn