Synthesis of a Bench-Stable Manganese(III) Chloride Compound: Coordination Chemistry and Alkene Dichlorination.

The complex [MnCl(OPPh)] () is a bench-stable and easily prepared source of MnCl. It is prepared by treating acetonitrile solvated MnCl () with PhPO and collecting the resulting blue precipitate. is useful in coordination reactions by virtue of the labile PhPO ligands, and this is demonstrated through the synthesis of {Tpm*}MnCl (). In addition, methodologies in synthesis that rely on difficult or cumbersome to prepare solutions of reactive MnCl can be accomplished using instead. This is demonstrated through alkene dichlorinations in a wide range of solvents, open to air, and with good substrate scope. Light-accelerated halogenation and radical sensitive experiments support a radical mechanism involving stepwise Cl-atom transfer(s) from .