Abstract

While the activation of alkynes by ruthenium(II) and osmium(II) bis-diphosphine complexes in the form of [RuII/OsII(P^P)2X2] has been studied for nearly three decades and are known to give a variety of metal−vinylidene, −allenylidene, and −alkynyl complexes, recent findings on the isolation of unprecedented organometallic complexes from alkynes and [RuII/OsII(P^P)2X2] suggest the existence of unconventional reaction pathways which have been largely overlooked. In this focused review, a brief overview on the conventional reactivities between alkynes and cis-[RuII/OsII(dppm)2Cl2] (dppm = 1,2-bis(diphenylphosphino)methane) will first be provided, which is then followed by discussions on the recent discoveries of the unconventional reactivities with emphasis on the mechanistic insights into the Ru/Os-induced alkyne transformations.

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