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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

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00216a019· OSTI ID:5918207
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The reactions of anhydrous HBr and HCl with trans-(Mo(N/sub 2/)/sub 2/(triphos)(PR/sub 3/)), where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/(PR/sub 3/ = PPh/sub 3/(1), PMePh/sub 2/ (2)), in tetrahydrofuran (THF) solution to produce ammonia and in benzene solution to produce hydrazine and ammonia have been examined. Complex 1 reacted with HBr in THF to produce 1.5 mol of N/sub 2//mol of 1 and routinely ca. 0.72 mol of NH/sub 3//mol of 1, respectively, and MoBr/sub 3/(triphos) (greater than or equal to94% yield). No more than a trace of hydrazine was detected. Total nitrogen balance was increased to 100% when amounts of HBr were added periodically during the reaction. The reaction of 1 or 2 with HBr or HCl led to the rapid loss of 1 mol of N/sub 2/ and the formation of a pair of isomeric hydrazido(2-) complexes, (MoX(NNH/sub 2/)(triphos)(PR/sub 3/))X (PR/sub 3/ = PPh/sub 3/ for 1 A(X) and 1 B(X), PPh/sub 2/Me for 2A(X) and 2B(X); X = Br, Cl). The same mixtures were formed in the absence of solvent. The presence of two isomers was the result of the position of the phenyl group on the central phosphorus atom of the triphos ligand relative to the hydrazido(2-) ligand. 48 references, 3 figures, 3 tables.
Research Organization:
Univ. of Nebraska, Lincoln
OSTI ID:
5918207
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:22; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

090320* -- Inorganic Hydrogen Compound Fuels-- Preparation-- (1976-1989)
10 SYNTHETIC FUELS
AMMONIA
AROMATICS
BENZENE
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
DATA
ENZYMES
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC COMPOUNDS
HYDRAZINE
HYDRIDES
HYDROBROMIC ACID
HYDROCARBONS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
ISOMERS
KINETICS
MAGNETIC RESONANCE
MOLYBDENUM COMPLEXES
NITRO-GROUP DEHYDROGENASES
NITROGEN COMPLEXES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NITROGENASE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDOREDUCTASES
REACTION INTERMEDIATES
REACTION KINETICS
RESONANCE
SOLVENTS
SPECTRA
SYNTHESIS
TETRAHYDROFURAN
TRANSITION ELEMENT COMPLEXES
YIELDS