CONVERSION OF A MANGANESE-CARBON-BONDED COMPLEX TO A MANGANESE-OXYGEN-BONDED COMPLEX, SOME REACTIONS OF MANGANESE CARBONATO COMPLEXES

Stirring a solution of the manganese carboxylate, (dppe)(CO)(3)Mn-C(O) OCH3, 1, in dichloromethane saturated with water converts it to the br idging carbonato complex, (dppe)(CO)(3)Mn-OC(O)O-Mn(CO)(3)(dppe), 2. T his multi-step con vers ion involves the in-situ transformation of a M n-C bonded complex to a Mn-O bonded one. When 2 is stirred with HCl, i t is converted quantitatively to the covalent chloride (dppe)(CO)(3)Mn -Cl, 11, with evolution of carbon dioxide. Similar HCl treatment of th e manganese carboxylate 1 gives three compounds: the same covalent chl oride, 11; the ionic chloride, [(dppe)(CO)(4)Mn]Cl-+(-), 12, and the h ydride, (dppe)(CO)(3)Mn-H, 5. Reasonable schemes for these conversions are suggested. Heating the ionic chloride complex to its melting poin t converts it to the covalent chloride complex; the same transformatio n is accomplished by refluxing the ionic chloride in acetonitrile. (C) 1997 Elsevier Science S.A.