The reactions of Na[Mn(CO)5] or Na[Mn(CO)4(PPh3)] with CH2ClI yield the new chloromethyl complexes Mn(CO)5CH2Cl and Mn(CO)4(PPh3)CH2Cl. Reaction of Na[Re(CO)5] or Na[CpRu(CO)2] with ClCH2OMe yields Re(CO)5CH2Cl and CpRu(CO)2CH2Cl respectively, in addition to the corresponding methoxymethyl complexes (Cp = η5-C5H5). Reaction of CpRu(CO)2CH2OMe with HCl yields the corresponding chloromethyl complex.