โ Scribed by Lisa McElwee-White; Kevin B. Kingsbury; John D. Carter
No coin nor oath required. For personal study only.
Photo-oxidation of the metal carbyne complexes ($-C?'Hs)LILM=CR (M =Mo, W, L,, b=CO, P(OMej3; R=phenyl, cyclopropyl) generates radical cations that are extremely reactive. Depending on the reaction conditions, either the oxidized species exhibit the ligand exchange and atom abstraction processes typical of metal radicals, or the carbyne tigands undergo a series of highly unusual rearrangements to yield organic products. For the cyciopropyl carbynes ($-C,H,)P(OMe),M=C(c-r&H,), photo-oxidation in the absence of added ligands results in the formation of cyclopentenone. When substituents are present on the cyclopropyl ring, single regioisomers or stereoisomers of the resulting cyclopentenones are produced.
๐ SIMILAR VOLUMES
The partial conversion of alkanes to the corresponding ketones has been achieved byirradiation of a suspension of semiconductor powder in oxygen-saturated alkanes. The reactivity of thermally and chemicallydoped semiconductor and the effect of chemisorbed water have also been studied.
Metal-carbynes RCzM(C0)4Rr with diacetylenes give specific phenols in good yield. The reactions take only a few minutes at or below room temperature. Metal-carbynes, unlike metal-carbenes, 1 have rarely been considered reagents for organic