Reactions of hydridocarbonylstris(triphenylphosphine)rhodium with alkynes
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Add time:08/26/2019 Source:sciencedirect.com
The hydride, RhH(CO)(PPh3)3, reacts with the alkynes RC2R (where = CO2Me, CO2Et, CO2H or C6H5), to give stable adducts of the type RCH=CR-Rh-(CO)(PPH3_2. Cleavage of the adducts where R = CO2Me or C6H5 with anhydrous HCl gives dimethyl fumarate and trans-stilbene respectively, indicating that these adducts have a trans-configuration about the double bond. The similar reaction of the hydride with perfluoro-1-butyne also gives a stable, crystalline adduct, CF3-CH=C(CF3)-Rh(CO)(PPH3),2, which has been shown by NMR spectroscopy to have a cis-configuration, implying that a different mechanism operates in this reaction.
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