Reactions of coordinated dinitrogen. 8. Formation of ammonia by protonation of a molybdenum-dinitrogen complex and isolation and characterization of the molybdenum-containing product

Journal Article · Wed Sep 10 04:00:00 EDT 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00539a035· OSTI ID:6841152

Baumann, J A; George, T A

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), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:19; ISSN JACSA
• Country of Publication: United States
• Language: English

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AMMONIA
AMMONIUM COMPOUNDS
AROMATICS
BROMIDES
BROMINE COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
MOLECULAR STRUCTURE
MOLYBDENUM COMPOUNDS
NITROGEN COMPLEXES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS