Mononuclear manganese carbonyl

Group VIIA (Mn, Tc. Re). A number of mononuclear manganese carbonyl derivatives have been y- irradiated and examined by e.s.r. spectroscopy. The motivation behind much of this effort was the search for the elusive radical Mn(CO)s. The e.s.r. spectrum of this species is now firmly (35-37) established (Figure 4), although there is still some suggestion that the true "naked Mn(CO)s has yet to be observed (37). 

Organometallic Molecules.— With one exception, all the complexes in this section are manganese carbonyls. They are mostly mononuclear and with octahedral geometry around the manganese atom. 

The synthesis of pentacarbonyl rhenium(I) halides, Re(CO)5X, succeeded from simple and complex rhenium halides below 200 atm of CO at 200° C. The compounds are extraordinarily stable and form easily, often quantitatively, from carbon monoxide and rhenium metal in the presence of other heavy metal halides or halogen sources such as CC14. Later we prepared the corresponding carbonyl halides of manganese (67) and technetium (68) from their respective carbonyls. It was found that the corresponding binuclear tetracarbonyl halides [M(CO)4X]2 (M = Mn, Re) could be made by heating the mononuclear M(CO)5X complexes (15, 69), as well as by other methods. 

The first mononuclear carbonyl compound of cobalt, iron or manganese known was the pentacarbonyl complex [Fe(CO)5] " with a trigonal-bipyramidal ligand field (see Fig. 2). Though related electroneutral species of cobalt and manganese are not known due to a strict observance of the 18-electron-rule in these cases, the monoanionic manganese derivative fMn(CO)5] has also been described as a trigonal-bipyramidal species. ... 

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