(η⁵-Cyclopentadienyl)Tricarbonylmanganese(I) Complexes

Since the initial preparation of (η5-C5H5)Mn(CO)3 by Fischer and Jira in 1954, many methods have been developed for the synthesis of this compound (often referred to as "cymantrene") and its C5 substituted derivatives. Interestingly, each of these preparations has at least one significant drawback from a preparative perspective (thallium reagents, high pressures, poor yields, or reactants that require significant preparative investment). Surprisingly missing from this collection of preparative methods is the direct reaction between commercially available Mn(CO)5Br and NaC5H5. In 1988, however, Smart and coworkers found MnBr(CO)3(pyridine)2 to be an effective reagent in making a substituted indacenylmanganese tricarbonyl complex. As this pyridine complex also serves as an effective manganese starting material, this chapter discusses the high-yield syntheses of cymantrene and its derivatives such as (η5-C5Me5)Mn(CO)3.