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Reductions of metal carbonyls by quaternary ammonium borohydrides

1981; Elsevier BV; Volume: 218; Issue: 3 Linguagem: Inglês

10.1016/s0022-328x(00)81005-0

1872-8561

Dorothy H. Gibson, Fahim Ahmed, Kenneth R. Phillips,

Coordination Chemistry and Organometallics

Quaternary ammonium borohydrides, used directly or generated in phase transfer reactions, are highly effective reagents for preparing metal carbonyl anions from metal carbonyls [Mo(CO)6, Mn2(CO)10, Re2(CO)10, CO2(CO)8, Fe3(CO)12, Ru3(CO)12 and (η5-C5H5)2Mo2(CO)6] and from some metal carbonyl halides [BrMn(CO)5 and η5-C5H5Mo(CO)3Cl]. Where strongly basic anions would be formed from a halide [BrMn(CO)4PPh3 and η5-C5H5Ru(CO)2Br], the reactions provide efficient syntheses of the corresponding hydrides instead. The anion η5-C5H5Fe(CO)2− is not accessible by these techniques; reaction of η5-C5H5Fe(CO)2Br yields the iron dimer (via the highly nucleophilic anion) and the dimer is unreactive toward Q+BH4−. Reductions of Re2(CO)10 conducted in CH2Cl2 provide Re2(CO)9Cl− in high yield.