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A useful intermediate for organorhenium complexes is the alkyne complex 2, which can be formed from the tetrachloride 1. In the presence of catalytic amounts of HBF42 can undergo reaction with ethene and 2-butene to give the 1,3-diene complexes 3 and 4 respectively. Cl/ligand exchange is observed with 1-butyne and acetonitrile in the presence of equimolar amounts of HBF4, but no C[BOND]C bond formation occurs.