182002-80-8Relevant articles and documents
Intermediates and anion effects in the activation of carbon-fluorine bonds by η5-pentamethylcyclopentadienylrhodium halide complexes; Crystal structure of [{η5-C5Me3[CH2C 6F4P(C6F5)CH2] 2-1,3}RhBr]+·Br-
Atherton, Malcolm J.,Fawcett, John,Holloway, John H.,Hope, Eric G.,Russell, David R.,Saunders, Graham C.
, p. 163 - 172 (2007/10/03)
The reaction between [(η5-C5Me5)RhBr(μ-Br)]2 and the diphosphine, (C6F5)2PCH2CH2P(C 6F5)2 (dfppe), in benzene proceeded via the intermediate cation [(η5-C5Me5)RhBr(dfppe)]+, which underwent C-F and C-H bond activation and C-C bond formation to give sequentially [{η5-C5Me4CH2C6F 4P(C6F5)CH2CH2P(C 6F5)2}RhBr]+ and then [{η5-C5Me3[CH2C 6F4P(C6F5)CH2] 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 P1 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 R1 and wR2 [I=2σ(I)] values of 0.0581 and 0.1641, respectively, for 6837 unique reflections. In contrast to the BF4- salt, the Cl- and BPh4- salts of cation [(η5-C5Me5)RhCl(dfppe)]+ undergo reaction upon thermolysis in benzene to give the cation [{η5-C5Me3[CH2C 6F4P(C6F5)CH2] 2-1,3}RhCl]+.