207990-44-1Relevant articles and documents
Carbon-fluorine bond activation in the reactions between 1,2-bis[bis-(2,6-difluorophenyl)phosphino]ethane and [{MCl(μ-Cl)(η5-C5Me5)}2] (M = Rh or Ir)
Fawcett, John,Friedrichs, Steffi,Holloway, John H.,Hope, Eric G.,McKee, Vickie,Nieuwenhuyzen, Mark,Russell, David R.,Saunders, Graham C.
, p. 1477 - 1484 (1998)
The new fluorine-containing diphosphine (C6H3F2-2,6)2PCH2CH 2P(C6H3F2-2,6)2 I has been prepared and structurally characterized by single-crystal X-ray diffraction. The reaction between [{RhCl(μ-Cl)(η5-C5Me5)}2] and I in refluxing benzene yielded the cationic species [RhCl{η5-C5Me3[(2-CH2C 6H3F-6)P(C6H3F 2-2,6)CH2]2-1,3}]+, which was characterized as the BF4- salt 1. The reaction involved the regiospecific activation of two C-F bonds and two C-H bonds and the formation of two C-C bonds. In contrast, the reaction between [{IrCl(μ-Cl)-(η5-C5Me5)}2] and I did not involve C-F bond activation, but resulted in the formation of the dinuclear complex [{IrCl2(η5-C5Me5)[P(C 6H3F2-2,6)2CH2]} 2] 2, the characterization of which was confirmed by the synthesis of the (C6F5)2PCH2CH2P(C 6F5)2 analogue [{IrCl2(η5-C5Me5)[P(C 6F5)2CH2]}2] 3. The complexes [MCl{(C6H3F2-2,6)2PCH 2CH2P(C6H3F2-2,6) 2}(η5-C5Me5)]+BF 4- (M = Rh 4 or Ir 5), unlike their (C6F5)2PCH2CH2P(C 6F5)2 analogues, did not undergo C-F and C-H bond activation and C-C bond formation on thermolysis. The structures of complexes 2-4 have been determined by single-crystal X-ray diffraction.
