STEREOSPECIFIC SYNTHESES OF NEW MANGANESE(I) ISOCYANIDE DERIVATIVES

Three series of cationic manganese(I) carbonyls are reported: [Mn(CO)5-n(CNMe)n(CNPh)]PF6 (n = 1 → 4), [Mn(CO)5-n(CNMe)(CNPh)n]PF6 (n = 1 → 4), and [Mn(dpe)(CO)4-n(CNMe)n]PF6 (n = 1 → 4). Most of these compounds were prepared from a substituted metal carbonyl halide by replacement of halide ion by an added ligand (CNR or CO), such reactions requiring an added halide ion acceptor (Ag+ or AlCl3). The added ligand enters the site of departing halide ion. It was possible to prepare isomers of many compounds reported, taking advantage of this stereospecificity. Structures of the products were defined, often unequivocally, by infrared and nmr spectroscopic data. Cyclic voltammetry showed that these compounds undergo one electron oxidations, the ease of oxidation determined by the nature of the ligand groups and the stereochemistry. © 1979.