Direct Syntheses of 1-Phenylphosphetane and 1-Phenylphosphirane. Crystal and Molecular Structures of Neutral and Cationic Cyclotrimerization Precursor Complexes
| Autor: | Mark A. McDonald, Michael Pabel, David C. R. Hockless, and Anthony C. Willis, S. Bruce Wild, Yew Beng Kang |
|---|---|
| Rok vydání: | 1996 |
| Předmět: |
chemistry.chemical_classification
Diethyl sulfide Organic Chemistry Inorganic chemistry Cationic polymerization chemistry.chemical_element Polymer Inorganic Chemistry Dilithium Crystal Crystallography chemistry.chemical_compound chemistry Molybdenum Physical and Theoretical Chemistry Benzene Palladium |
| Zdroj: | Organometallics. 15:1301-1306 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om9507336 |
| Popis: | Dilithium phenylphosphide reacts with 1,3-dichloropropane or 1,2-dichloroethane to give 1-phenylphosphetane (1) or 1-phenylphosphirane (2), respectively, both of which can be isolated by distillation in vacuo. The phosphetane rapidly polymerizes when neat but is stable in benzene wherefrom the polymer can be selectively and quantitatively separated from 1 by the addition of trans-dichlorobis(diethyl sulfide)palladium(II). Four-membered 1 has a remarkably low-field 31P NMR chemical shift (13.9 ppm), and 2, a remarkably high-field shift (−236 ppm). The crystal and molecular structures of the potential cyclotrimerization precursor complexes fac-[Mo(CO)3(1)3] (7), fac-[Mo(CO)3(2)3] (8), and [(η5-C5H5)Fe(2)3]PF6 (9) have been determined. Both molybdenum complexes have C3 symmetry in the solid state, and the iron complex has C1 symmetry. An interesting feature of the three structures is that the phenyl groups of the small phosphorus heterocycles in each case are arranged in groups of three syn or anti to the au... |
| Databáze: | OpenAIRE |
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