Competition between cluster fragmentation, C–C bond coupling and C–X bond activation in silver hexynyl cluster cations, [(C4H9CCAg)nAg]+. Size does matter!

Silver hexynyl cluster cations, [(C4H9CCAg)nAg]+, exhibit a rich unimolecular chemistry that is dependant on the cluster size, n (1–5), cluster fragmentation (for all n > 1); C–C bond coupling (n = 3 & 4); C–H bond activation with comcomitant silver hydride formation (n = 1 & 4); C–C bond activation (n = 1 & 4).