Metal-Metal Bond Fission and the Formation of Triosmium-Alkene Complexes via the Reaction of 3-η2-CF3C=C(H)CF3>(CO)10> with Nucleophiles; A Complete Model for the Catalytic Reduction of an Alkyne to an Alkene by a Cluster

DOI: 10.1039/DT9840001931

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1931 - 1936 (1984)

Update date:2022-08-05

Topics: nucleophiles

Authors:

Dawoodi, Zain

Mays, Martin J.

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Article abstract of DOI:10.1039/DT9840001931

The reaction of with hexafluorobut-2-yne gives the complex 3-η²-CF3C=C(H)CF3>(CO)10> in 88percent yield.The reactions of this complex with a variety of nucleophiles have been investigated and have led to the preparation of a series of stable fluoro-alkene complexes (CO)10Y> (Y = PEt3, CO, Cl(1-), Br(1-), I(1-), or H(1-)).For Y = PEt3 and CO both the cis- and trans-fluoro-alkene complexes are formed in approximately equimolar proportions, but the other nucleophiles give only a single fluoro-alkene complex which, for Y = Br(1-), is the trans product.The major product of the reaction with Y = PEt3 results from metal-metal bond cleavage to give the complex 2-CF3C=C(H)CF3>(CO)10(PEt3)> which contains a bent chain of Os atoms and a terminal Os-H ligand.The reactions of 3-η²-CF3C=C(H)CF3>(CO)10> with nucleophiles are compared with those of the unsubstituted vinyl complex 2-CH=CH2)(CO)10>, and a model is proposed for the catalytic reduction of an alkyne to an alkene by a trinuclear osmium cluster.

Full text of DOI:10.1039/DT9840001931

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