Reactions of coordinated dinitrogen. 8. Formation of ammonia by protonation of a molybdenum-dinitrogen complex and isolation and characterization of the molybdenum-containing product
This is the first reported conversion of metal-coordinated dinitrogen into ammonia in which the fate of the metal has been determined. This reaction is shown in the following equation, where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ and L = PPh/sub 3/:2Mo(N/sub 2/)/sub 2/(triphos)(L) + 8HBr ..-->.. 2NH/sub 4/Br + 2MoBr/sub 3/(triphos) + 3N/sub 2/ + 2L. The metal complex which is a new subclass of bis(dinitrogen) complexes of molybdenum, reacted in tetrahydrofuran (THF) solution with anhydrous hydrogen bromide to produce ammonium bromide. No hydrazine or hydrazinium bromide was detected among the reaction products. Ammonium bromide was detected by infrared spectroscopy among the reaction products after solvent and excess HBr had been removed in vacuo. The yield of ammonia was determined quantitatively by the indophenol method after either aqueous, nonaqueous (ethanol), or two-phase (dichloromethane-water) extraction of ammonium bromide from the residue. The molybdenum-containing product slowly decomposed during the dichloromethane-water extraction step. Isolation of pure MoBr/sub 3/(triphos) was carried out in a separate experiment in which only N/sub 2/ evolution was measured. All volatiles were removed from the reaction vessel and the resulting yellow solid was washed with ethanol and dried. Its identity was confirmed by elemental analysis.
- Research Organization:
- Univ. of Nebraska, Lincoln
- OSTI ID:
- 6841152
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 102:19
- Country of Publication:
- United States
- Language:
- English
Similar Records
Formation of ammonia and hydrazine from the reactions of acids with bis(dinitrogen) complexes of molybdenum. Identification and isolation of intermediates. Possible analogy with the hydrazine-forming property of nitrogenase
Synthesis of mono(dinitrogen) complexes of molybdenum. Formation of ammonia and hydrazine
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
AMMONIA
CHEMICAL PREPARATION
MOLYBDENUM COMPOUNDS
CHEMICAL REACTIONS
MOLECULAR STRUCTURE
NITROGEN COMPLEXES
AMMONIUM COMPOUNDS
AROMATICS
BROMIDES
ORGANIC PHOSPHORUS COMPOUNDS
BROMINE COMPOUNDS
COMPLEXES
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
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