Journal of Organometallic Chemistry p. 69 - 78 (1996)
Update date:2022-08-05
Topics:
Toreki, Robert
Schrock, Richard R.
Davis, William M.
Photolysis of compounds of the type [Re(CCMe2R)(OR′)2]2 (R = Me or Ph; OR′ = OtBu, OCMe2(CF3), or OCMe(CF3)2) in benzene with a medium pressure mercury lamp yields compounds of the type [Re(OR′)2]2(μ-CCMe2R)2 in an intramolecular and irreversible manner. [Re(CCMe2R)(OR′)2]2 and [Re(OR′)2]2(μ-CCMe2R)2 (OR′ = OtBu or OCMe2(CF3)2) both react with excess carbon monoxide in several solvents to afford the dimers [Re(OR′)2(CO)]2(μ-CCMe2R)2 quantitatively. An X-ray study of [Re(OtBu)2(CO)]2(μ-CtBu) 2 shows it to consist of two distorted trigonal bipyramids connected by two symmetrically bridging neopentylidyne ligands. The unbridged dimers of general formula [Re(CCMe2R)(OR′)2]2 do not react readily with simple substrates such as phosphines, olefins, or acetylenes, although [Re(CCMe2R)(OtBu)2]2 can be oxidized by iodine to yield Re(CCMe2R)(OtBu)2I2 in good yield. In contrast, {Re[OCMe(CF3)2]2}2 (μ-CtBu)2 reacts with one equivalent of phenylacetylene to give a species in which one of the two bridging alkylidyne ligands is retained.
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