Conversion of a manganese-carbon-bonded complex to a manganese-oxygen-bonded complex, some reactions of manganese carbonato complexes

Article abstract of DOI:10.1016/S0022-328X(97)00486-5

Stirring a solution of the manganese carboxylate, (dppe)(CO)₃Mn-C(O)OCH₃, 1, in dichloromethane saturated with water converts it to the bridging carbonato complex, (dppe)(CO)₃Mn-OC(O)O-Mn(CO)₃(dppe), 2. This multi-step conversion involves the in-situ transformation of a Mn-C bonded complex to a Mn-O bonded one. When 2 is stirred with HCl, it is converted quantitatively to the covalent chloride (dppe)(CO)₃Mn-Cl, 11, with evolution of carbon dioxide. Similar HCl treatment of the manganese carboxylate 1 gives three compounds: the same covalent chloride, 11; the ionic chloride, [(dppe)(CO)₄Mn] ⁺ Cl^-, 12, and the hydride, (dppe)(CO)₃Mn-H, 5. Reasonable schemes for these conversions are suggested. Heating the ionic chloride complex to its melting point converts it to the covalent chloride complex; the same transformation is accomplished by refluxing the ionic chloride in acetonitrile.