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

• Published in: Journal of the American Chemical Society 2022-09, Vol.144 (37), p.16761-16766
• Main Authors: Saju, Ananya, Griffiths, Justin R., MacMillan, Samantha N., Lacy, David C.
• Format: Article
• Language: English
• Subjects: Acetonitriles; Alkenes; Chlorides; Halogens; Ligands; Manganese; Solvents
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.2c08509

The complex [MnCl3(OPPh3)2] (1) is a bench-stable and easily prepared source of MnCl3. It is prepared by treating acetonitrile solvated MnCl3 (2) with Ph3PO and collecting the resulting blue precipitate. 1 is useful in coordination reactions by virtue of the labile Ph3PO ligands, and this is demonstrated through the synthesis of {Tpm*}­MnCl3 (3). In addition, methodologies in synthesis that rely on difficult or cumbersome to prepare solutions of reactive MnCl3 can be accomplished using 1 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 1.