Reactivity of [Cp∗Rh(η6-C6H3NH2-2,6-i-Pr2)](OTf)2 toward phosphines and alkynes

Fulvene–Ruthenium and Cp–Ruthenium Complexes via [2 + 2 + 1] Cyclotrimerization of Phenylacetylene with [RuCl(Tp)(1,5-cod)]

“…Prior to use, solvents were purified following the standard procedures . Synthetic experiments were carried out under an argon atmosphere using standard Schlenk techniques. , Solvents were dried prior to use using standard techniques .…”

“…19 Alkyne cyclotrimerization reactions in general have been found to occur mainly for the group 9 and 10 transition metals Co, Rh, Ni, and Pd. 13 The formation of five-membered carbocycles from phenylacetylene, in particular, have only been reported for the late-transition-metal complexes of rhodium, 23,24 iridium, 21 and palladium 25,26 23 Our research has focused on the organometallic chemistry involving the dimerization, cyclotrimerization, and cyclooligomerization of alkynes using ruthenium(II) systems. During these studies, routes to novel ruthenium(II)−cyclopentatrienyl complexes were defined.…”

“…Alkyne cyclotrimerization reactions in general have been found to occur mainly for the group 9 and 10 transition metals Co, Rh, Ni, and Pd . The formation of five-membered carbocycles from phenylacetylene, in particular, have only been reported for the late-transition-metal complexes of rhodium, , iridium, and palladium , through the formal [2 + 2 + 1] cyclotrimerization route. Specific mention could be made of the reaction of [Rh(Cp*)­(η 6 -2,6-(MeCH) 2 ­C 6 H 3 NH 2 )]­(OTf) 2 with the terminal aryl alkynes HCCPh and HCCC 6 H 4 CH 3 in alcohol (EtOH, n -BuOH), which gave the five-membered cycloadducts [Rh(Cp*)­(η 5 -C 5 H 2 Ar 2 -CH(Ar)­OEt)]­OTf (Ar = Ph, p -tolyl) via a [2 + 2 + 1] cyclotrimerization mechanism …”