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The catalytic substitution of phosphines for halide on CpFe(CO) 2 X (X = Cl, Br, I) has been shown to proceed through an electron transfer chain catalysis mechanism. The reaction may be initiated by CpFe(CO) 2 (PR 3 ) . generated by photochemical or thermal cleavage of [CpFe(CO) 2 ] 2 or by addition of catalytic amounts of other strong reductants.