Reactions involving transition metals: XX. A comparison of the reactions of 1,2,3,4,7,7-hexafluorobicyclo[2.2.1]heptadiene,and 2,3-bis(trimethyltin)- and 2,3-dichloro-1,4,5,6,7,7-hexafluorobicyclo[2.2.1]hepta-2,5-dienes with low valent transition metal complexes |
| |
| Authors: | Brian L Booth Sylvia Casey Robert P Critchley Robert N Haszeldine |
| |
| Institution: | Department of Chemistry, University of Manchester Institute of Science and Technology, Manchester M60 1QD Great Britain |
| |
| Abstract: | 1,2,3,4,7,7-Hexafluorobicyclo2.2.1]heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo2.2.1]hepta-2,5-diene (2) react with M(Ph3P)4] (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo2.2.1]hepta-2,5-diene (3) gives only PtCl2(PPh3)2] with Pt(Ph3P)4], but a low yield of an adduct was obtained with Pd(PPh3)4]. The diene 1 also reacts with Fe(CO)5 to form the complex (C7H2F6)Fe(CO)4], and with Rh(C2H4)2(acac)] to give (C7H2F6)Rh(acac)] in which the diene acts as a bidentate ligand. Similar products could not be isolated from the reactions of 2 and 3. A stable adduct, believed to be {C7F6(SnMe3)2}Rh(CO)2(μ-Cl)2Rh(CO)2] has been isolated from the reaction between 2 and Rh(CO)2Cl]2. This adduct reacts with PPh3 to give the bridge-cleavage product {C7F6(SnMe3)2}RhCl(CO)(PPh3)2]. Reaction of 1 with Rh(CO)2Cl]2 gives an unstable adduct which could not be isolated, and 2 does not react at room temperature. The chloro derivative 3 reacts with PdCl2(PhCN)2] to give the adduct (C7F6Cl2)PdCl(PhCN)], but 1 and 2 do not react under similar conditions. Stable substitution products (C7F6R2)M] (R = H, M = Fe(CO)2(η-C5H5); R = SnMe3, M = Fe(CO)2(η-C5H5), Mn(CO)5, Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2; R = Cl, M = Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2) have been isolated from the reactions of the dienes with carbonylmetal anions. Insertion of the CHCH bond occurs when 1 is heated with MnMe(CO)5] to give {C7F6H2C(n(CO)4], and this, on reaction with either PPh3 or Pt(PPh3)4], gives (C7F6H2COMe)Mn(CO)4PPh3]. |
| |
| Keywords: | Author to whom enquiries should be addressed |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
