Reactions of Hydride Complexes of Ruthenium(II) with Alkynes

DOI: 10.1039/DT9890000589

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 589 - 594 (1989)

Update date:2022-07-29

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Authors:

Bray, Joanne M.

Mawby, Roger J.

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Article abstract of DOI:10.1039/DT9890000589

The complex reacts with alkynes RC<*>CR' (R=H, R'=Ph or CMe3; R=R'=CO2Me) to yield vinyl complexes .Addition of Ru-H across the alkyne triple bond is cis for HC<*>CPh and HC<*>CCMe3, but may be trans for MeO2CC<*>CCO2Me.The dihydride hydrogenates alkynes HC<*>CR (R=Ph or CMe3) to H2C=CHR and PhC<*>CPh to cis-PhCH=CHPh, with the accompanying formation of alkynyl complexes CR)H(PMe2Ph)2> and the alkyne complex CPh)(PMe2Ph)2> respectively.The reaction sequence is believed to involve rate-determining formation of vinyl hydride complexes by addition of Ru-H to the alkyne, followed by rapid alkene elimination and reaction of with a second molecule of alkyne.With MeO2CC<*>CCO2Me, the complexes (L=PMe2Ph or AsMe2Ph) form long-lived vinyl hydride complexes which exist in solution as mixtures of conformers.

Full text of DOI:10.1039/DT9890000589

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