Intermediates and anion effects in the activation of carbon–fluorine bonds by η5-pentamethylcyclopentadienylrhodium halide complexes; crystal structure of [{η5-C5Me3[CH2C6F4P(C6F5)CH2]2-1,3}RhBr]+·Br−
| Autor: | Graham C. Saunders, Malcolm J. Atherton, Eric G. Hope, David R. Russell, John H. Holloway, John Fawcett |
|---|---|
| Rok vydání: | 1999 |
| Předmět: |
Organic Chemistry
Thermal decomposition chemistry.chemical_element Halide Nuclear magnetic resonance spectroscopy Crystal structure Triclinic crystal system Biochemistry Rhodium Ion Inorganic Chemistry Crystallography chemistry.chemical_compound chemistry Materials Chemistry Physical and Theoretical Chemistry Benzene |
| Zdroj: | Journal of Organometallic Chemistry. 582:163-172 |
| ISSN: | 0022-328X |
| Popis: | The reaction between [(η 5 -C 5 Me 5 )RhBr(μ-Br)] 2 and the diphosphine, (C 6 F 5 ) 2 PCH 2 CH 2 P(C 6 F 5 ) 2 (dfppe), in benzene proceeded via the intermediate cation [(η 5 -C 5 Me 5 )RhBr(dfppe)] + , which underwent CF and CH bond activation and CC bond formation to give sequentially [{η 5 -C 5 Me 4 CH 2 C 6 F 4 P(C 6 F 5 )CH 2 CH 2 P(C 6 F 5 ) 2 }RhBr] + and then [{η 5 -C 5 Me 3 [CH 2 C 6 F 4 P(C 6 F 5 )CH 2 ] 2 -1,3}RhBr] + , as evidenced by mass spectrometry and NMR spectroscopy. The bromide salt of the final product ( 4c ) has been structurally characterized by X-ray diffraction. Compound 4c crystallizes in the triclinic space group P with a =10.616(1), b =13.904(2), c =14.911(1) A, α =66.86(1), β =86.38(1), γ =84.72(1)° and Z =2. Refinement gave final R 1 and wR 2 [ I =2 σ ( I )] values of 0.0581 and 0.1641, respectively, for 6837 unique reflections. In contrast to the BF 4 − salt, the Cl − and BPh 4 − salts of cation [(η 5 -C 5 Me 5 )RhCl(dfppe)] + undergo reaction upon thermolysis in benzene to give the cation [{η 5 -C 5 Me 3 [CH 2 C 6 F 4 P(C 6 F 5 )CH 2 ] 2 -1,3}RhCl] + . |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect