Journal of Organometallic Chemistry p. 363 - 376 (1982)
Update date:2022-09-26
Topics:
Baudry, Denise
Ephritikhine, Michael
Felkin, Hugh
L2ReH7 (L=PPh3) reacts smoothly with acyclic and cyclic dienes to give crystalline, air-stable, trihydrido-Η4-dienerhenium complexes L2(η4-diene)ReH3.The majority of these complexes are fluxional at room temperature; their NMR spectra suggest that at low temperature (-50 deg C) they are pentagonal bipyramidal, with the two phosphine ligands apical and the remaining ligands equatorial.Except for L2(η4-cyclopentadiene)ReH3, which readily loses dihydrogen to give L2(η5-C5H5)ReH, these diene trihydrides are thermally remarkably stable; L2(η4-cyclohexa-1,3-diene)ReH3 loses dihydrogen at >100 deg C to afford L2(η5-cyclohexadienyl)ReH2 and then L2(η6-C6H6)ReH, and L2(η4-butadiene)ReH3 and L2(η4-cycloocta-1,5-diene)ReH3 are stable in air up to 115 and 130 deg C, respectively.Protonation of the trihydrido-η4-diene complexes affords the corresponding saturated hydrocarbons and/or olefins.Hydrogenation of L2(η4-2,3-dimethylbutadiene)ReH3 regenerates the heptahydride L2ReH7.
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