Stirring a solution of the manganese carboxylate, (dppe)(CO) 3 Mn-C(O)OCH 3 , 1, in dichloromethane saturated with water converts it to the bridging carbonato complex, (dppe)(CO) 3 Mn-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) 3 Mn-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) 4 Mn] + Cl - , 12, and the hydride, (dppe)(CO) 3 Mn-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.