In the presence of triethylamine (NEt 3 ) and ethanol (EtOH), phenylethyne (or phenylacetylene, PhC≡CH) underwent cyclotrimerization: cis-dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium(II), [PdCl 2 (dppf)] (1), reacted with phenylethyne to give [Pd(dppf)(2,3,5-triphenylfulvene)] (2). Reaction of 2 with dimethyl acetylenedicarboxylate in dichloromethane gave [Pd(dppf)(CH 3 O 2 CC≡CCO 2 CH 3 )] (3) and a free 2,3,5-triphenylfulvene. Crystallographic data for 2.H 2 O: triclinic space group P1, a=10.658(2), b=10.896(2), c=21.080(3) 9, α=85.303(9) o , β=76.556(9) o , γ=80.447(10) o , Z=2, R(wR 2 )=0.0487(0.1083).