Abstract Cyclopentadienyl–ruthenium half-sandwich complexes with η 2-bound alkyne ligands have been suggested as catalytic intermediates in the early stages of Ru-catalyzed reactions with alkynes. We show that electronically unsaturated complexes of the formula [RuCl (Cp^)(η 2-RC≡ CR′)] can be stabilized and crystallized by using the sterically demanding cyclopentadienyl ligand Cp^(Cp^= η 5-1-methoxy-2, 4-tert-butyl-3-neopentyl- ...