205321-26-2Relevant articles and documents
Activation of C-F and C-H bonds by polyalkylcyclopentadienylrhodium complexes: Crystal structure of [(η5-C5Me4Et)RhCl{(C6F5)2PCH2CH2P(C6F5)2}]+·BF4-
Atherton, Malcolm J.,Fawcett, John,Holloway,Hope, Eric G.,Martin, Sinead M.,Russell, David R.,Saunders, Graham C.
, p. 67 - 79 (1998)
The reaction between [(η5-C5Me4Et)RhCl(μ-Cl)]2 and the diphosphine, (C6F5)2PCH2CH2P(C6F5)2 (dfppe), proceeded via the activation of two C-F and two C-H bonds and the formation of two C-C bonds to give a mixture of isomers of a salt with formulation '[(η5-C5Me4Et)RhCl{(C6F5)2PCH2CH2P(C6F5)2}-2HF]+·Cl-' (3a). Treatment of [(η5-C5Me4Et)RhCl(μ-Cl)]2 with NH4BF4 followed by dfppe yielded [(η5-C5Me4Et)RhCl{(C6F5)2PCH2CH2P(C6F5)2}]+·BF4- (4b) which, on thermolysis in ethanol underwent C-F and C-H bond activation to yield the tetrafluoroborate salt of 3a (3b). The structure of 4b was determined by a single crystal X-ray diffraction study. The salt 4b crystallizes in the triclinic space group P1 with a=15.743 (4), b=16.429 (2), c=16.970 (3) A, α=79.41 (2), β=84.34 (2), γ=82.01 (2)° and Z=4. Refinement gave final R1 and wR2[I>2σ(I)] values of 0.0955 and 0.2200 respectively for 7254 observed reflections. When the reaction between [(η5-C5Me4Et)RhCl(μ-Cl)]2 and dfppe was carried out in ethanol, a mixture of 3b, 4b and the singly C-F bond activated complex '[(η5-C5Me4Et)RhCl{(C6F5)2PCH2CH2P(C6F5)2}-HF]+·BF4-' (5b) were obtained after addition of NH4BF4. The monophosphines P(C6F5)3 and PPh(C6F5)2 failed to react with [(η5-C5Me5)RhCl(μ-Cl)]2 and the reaction between [(η5-C5Me5)RhCl(μ-Cl)]2 and PPh2(C6F5) did not lead to C-F bond activation but yielded (η5-C5Me5)RhCl2{PPh2( C6F5)} (6).
