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Reactivity of methacrylates in insertion polymerization
Polymerization of ethylene by complexes [{(P?O)PdMe(L)}] (P?O = kappa2-(P,O)-2-(2-MeOC6H4)2PC 6H4SO3)) affords homopolyethylene free of any methyl methacrylate (MMA)-derived units, even in the presence of substantial concentrations of MMA. In stoichiometric studies, reactive {(P?O)Pd(Me)L} fragments generated by halide abstraction from [({(P?O)Pd(Me)Cl}mu-Na) 2] insert MMA in a 1,2- as well as 2,1-mode. The 1,2-insertion product forms a stable five-membered chelate by coordination of the carbonyl group. Thermodynamic parameters for MMA insertion are DeltaH ? = 69.0(3.1) kJ mol-1 and DeltaS ? = -103(10) J mol-1 K-1 (total average for 1,2- and 2,1-insertion), in comparison to DeltaH? = 48.5(3.0) kJ mol-1 and DeltaS? = -138(7) J mol-1 K-1 for methyl acrylate (MA) insertion. These data agree with an observed at least 102-fold preference for MA incorporation vs MMA incorporation (not detected) under polymerization conditions. Copolymerization of ethylene with a bifunctional acrylate-methacrylate monomer yields linear polyethylenes with intact methacrylate substituents. Post-polymerization modification of the latter was exemplified by free-radical thiol addition and by cross-metathesis.
Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Safety of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium. In my other articles, you can also check out more blogs about 246047-72-3
Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI