Reactions of Acetylenes with Noble-metal Carbonyl Halides. Part 4. The Formation of a Platinaoxacyclopentenone Ring

DOI: 10.1039/DT9810002395

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2395 - 2404 (1981)

Update date:2022-07-30

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Authors:

Canziani, Franco

Garlaschelli, Luigi

Malatesta, Maria C.

Albinati, Alberto

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Article abstract of DOI:10.1039/DT9810002395

The compound (CO)Cl2> (1; R=Me or Et) reacts with water in polar solvents to give (2), containing a platinaoxacyclopentenone ring.In anhydrous conditions reacts with RO2CCCCO2R to give the insoluble polymeric species (7) which has been characterized both by conversion into (2) and by reaction with uni- and bi-dentate ligands to give (L=PPh3, PMePh2, or PEtPh2), , and , where the metallo-organic ring is preserved.No breaking of the ring was observed on reaction with chlorine and hydrochloric acid; conversely alkyl iodide gave (CO)I> which is readily converted into salt-like compounds of type (1) by reaction with Cl.A cyclisation mechanism is proposed for both the reaction in anhydrous conditions and that in the presence of water.Crystals of (2b) are triclinic, space group P1, with a=17.144(5), b=11.975(4), c=10.386(4) Angstroem, α=106.62(8), β=77.07(7), γ=95.94(7) deg, and Z=2.The crystal structure has been solved by the heavy-atom method from counter data and refined by least squares to a final R of 0.041 (for 3 055 observed reflections).The structure consists of discrete anionic and cationic counter ions, (+).

Full text of DOI:10.1039/DT9810002395

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