
Journal of the Chemical Society, Dalton Transactions p. 3215 - 3220 (1996)
Update date:2022-08-05
Topics:
Atherton, Malcolm J.
Fawcett, John
Holloway, John H.
Hope, Eric G.
Karacar, Atilla
Russell, David R.
Saunders, Graham C.
The reaction between [{M(η5-C5Me5)Cl(μ-Cl)}2] (M = Rh or Ir) and (C6F5)2PCH2CH2P(C 6F5)2 (dfppe) in refluxing benzene yielded the cationic species [M{η5-C5Me3[CH2C 6F4P(C6F5)CH2] 2-1,3}Cl]+ in which two C-F and two C-H bonds have been cleaved and two C-C bonds formed; HF is also produced. The complexes [M(η5-C5Me5)Cl(dfppe)]+BF 4- (M = Rh or Ir), which have not undergone C-F bond activation, were formed by treatment of [{M(η5-C5Me5)Cl(μ-Cl)}2] with NH4BF4. and dfppe, and have been structurally characterized by X-ray crystallography. Activation of the C-F bonds in these complexes is induced by thermolysis in refluxing ethanol. The reaction between [{M(η5-C5Me5)Cl(μ-Cl)}2] (M = Rh or Ir) and dfppe in refluxing ethanol yielded a mixture of the cations [M(η5-C5Me5)Cl(dfppe)]+, [M{η5-C5Me3[CH2C 6F4P(C6F5)CH2] 2-1,3}Cl]+ and, where M = Rh, the singly C-F bond-activated species [Rh{η5-C5Me4CH2C 6F4P(C6F5)CH2CH 2P(C6F5)2}Cl]+.
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