REACTIONS INVOLVING TRANSITION METALS. XX. A COMPARISON OF THE REACTIONS OF 1,2,3,4,7,7-HEXAFLUOROBICYCLOHEPTADIENE, AND 2,3-BIS(TRIMETHYLTIN)- AND 2,3-DICHLORO-1,4,5,6,7,7-HEXAFLUOROBICYCLOHEPTA-2,5-DIENES WITH LOW VALENT TRANSITION METAL COMPLEXES

Article abstract of DOI:10.1016/S0022-328X(00)83412-9

1,2,3,4,7,7-hexafluorobicyclo<2.2.1>heptadiene (1) and 2,3-bis(trimethyltin)-1,4,5,6,7,7-hexafluorobicyclo<2.2.1>hepta-2,5-diene (2) react with (M = Pt, Pd) to afford air-stable adducts. 2,3-Dichloro-1,4,5,6,7,7-hexafluorobicyclo<2.2.1>hepta-2,5-diene (3) gives only with , but a low yield of an adduct was obtained with .The diene 1 also reacts with Fe(CO)5 to form the complex <(C7H2F6)Fe(CO)4>, and with 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 <Rh(CO)2(μ-Cl)2Rh(CO)2> has been isolated from the reaction between 2 and 2.This adduct reacts with PPh3 to give the bridge-cleavage product <RhCl(CO)(PPh3)2>.Reaction of 1 with 2 gives an unstable adduct which could not be isolated, and 2 does not react at room temperature.The chloro derivative 3 reacts with 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 CH=CH bond occurs when 1 is heated with to give and this, on reaction with either PPh3 or , gives <(C7F6H2COMe)Mn(CO)4PPh3>.