| Autor: |
Fawcett, John, Friedrichs, Steffi, H. Holloway, John, G. Hope, Eric, McKee, Vickie, Nieuwenhuyzen, Mark, R. Russell, David, C. Saunders, Graham |
| Zdroj: |
Journal of the Chemical Society, Dalton Transactions; May 7, 1998, Vol. 1998 Issue: 9 p1477-1484, 8p |
| Abstrakt: |
The new fluorine-containing diphosphine (C6H3F2-2,6)2PCH2CH2P(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-CH2C6H3F-6)P(C6H3F2-2,6)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(C6H3F2-2,6)2CH2]}2] 2, the characterization of which was confirmed by the synthesis of the (C6F5)2PCH2CH2P(C6F5)2 analogue [{IrCl2(η5-C5Me5)[P(C6F5)2CH2]}2] 3. The complexes [MCl{(C6H3F2-2,6)2PCH2CH2P(C6H3F2-2,6)2}(η5-C5Me5)]+BF4– (M 4;= 4;Rh 4 or Ir 5), unlike their (C6F5)2PCH2CH2P(C6F5)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. |
| Databáze: |
Supplemental Index |
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