Abstract Silylation of either chloromethyl-or trichloromethylphosphonate in the presence of excess n-BuLi leads to the quantitative generation of lithiated trimethylsilyl- chloromethylphosphonates. This stable type of anion can be protonated, deuterated or alkylated. Compounds thus obtained can be desilylated in basic medium, or used for the preparation of α-bromo-and α-iodo-phosphonates after halogen-metal exchange. ...