Mechanistic Aspects of the Copolymerization of CO2 and Epoxides by Soluble Zinc Bis(phenoxide) Catalysts as Revealed by Their Cadmium Analogues
| Autor: | and J. D. Draper, Donald J. Darensbourg, Joseph H. Reibenspies, Sharon A. Niezgoda |
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| Rok vydání: | 1998 |
| Předmět: |
Steric effects
chemistry.chemical_element General Chemistry Zinc Biochemistry Medicinal chemistry Catalysis chemistry.chemical_compound Trigonal bipyramidal molecular geometry Colloid and Surface Chemistry Monomer chemistry Propylene carbonate Pyridine Organic chemistry Reactivity (chemistry) Xanthate |
| Zdroj: | Journal of the American Chemical Society. 120:4690-4698 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | A family of monomeric cadmium(II) phenoxides of the general formula Cd(O-2,6-R2C6H3)2(base)2-3 [R = Ph, tBu, Me; base = THF, THT, pyridine, propylene carbonate] has been synthesized. Determination of the solid-state structures of all complexes have uncovered a variety of geometries ranging from the expected distorted tetrahedral to square planar to trigonal bipyramidal, depending upon the identity of the phenoxide substituents and of the base ligands. By utilizing multinuclear NMR techniques available to cadmium, particularly 113Cd NMR, it was possible to discover the identities of these complexes in solution. Reactivities of these complexes with the small molecules CO2, COS, and CS2 were also carried out. While CO2 showed no reactivity with the sterically encumbered Cd(II) bis(phenoxides), insertion was observed spectroscopically to occur for COS and CS2. The product of CS2 insertion was isolated and characterized and found to be a dimeric xanthate complex, [Cd(S2CO-2,6-Ph2C6H3)]2[μ-O-2,6-Ph2C6H3]2. Thes... |
| Databáze: | OpenAIRE |
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