Backward synthesis of rhenium(I) γ-hydroxyvinylidene and γ-methoxyvinylidene complexes and their conversion to the allenylidene [Re{C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CCPh2}(CO)2(MeC(CH2PPh2)3)](OSO2CF3)
Abstract
The reactivity of the rhenium(I) allenylidene complex [Re{CCCPh2}(CO)2(triphos)](OTf) (1) [triphos = MeC(CH2PPh2)3] towards ionic nucleophiles and electrophiles has been explored. Nucleophiles regioselectively attack the Cγ carbon atom leading to the formation of σ-alkynyl complexes, while electrophiles attack the Cβ atom yielding carbyne complexes. The sequential addition of OH− and H+ to 1 at low temperature gave the γ-hydroxyvinylidene complex [Re{CC(H)C(OH)Ph2}(CO)2(triphos)](OTf) which regenerated 1 above −40 °C via H2O elimination.
![Graphical abstract: Backward synthesis of rhenium(I) γ-hydroxyvinylidene and γ-methoxyvinylidene complexes and their conversion to the allenylidene [Re{C [[double bond, length as m-dash]] C [[double bond, length as m-dash]] CPh2}(CO)2(MeC(CH2PPh2)3)](OSO2CF3)](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=B103293N&imageInfo.ImageIdentifier.Year=2001)
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![[double bond, length as m-dash]](https://www.rsc.org/images/entities/h2_char_e001.gif)
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