Synthesis of mono(dinitrogen) complexes of molybdenum. Formation of ammonia and hydrazine
The synthesis and reactivity of a series of mono-N/sub 2/ complexes of molybdenum are reported. Reduction of MoCl/sub 3/(triphos), where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/, with sodium amalgam in the presence of 2L or L/sub 2/ and with a regulated amount of N/sub 2/ led to the formation of Mo(N/sub 2/)(triphos)(L/sub 2/) (1-5): 1, L = PMe/sub 2/Ph; 2, L/sub 2/ = Me/sub 2/PCH/sub 2/PMe/sub 2/, dmpm; 3, L/sub 2/ = 1,2-(Me/sub 2/As)/sub 2/C/sub 6/H/sub 4/, diars; 4, L/sub 2/ = Ph/sub 2/PCH/sub 2/PPh/sub 2/, dppm; 5, L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/, dppe. Complexes 3 and 5 were each a mixture of two isomeric mono-N/sub 2/ complexes. Complexes 1-5 reacted with excess HX (X = Br, Cl) to afford varying yields of ammonia, hydrazine, and N/sub 2/ (and some H/sub 2/). Loss of N/sub 2/ occurred readily from 1 when it was evacuate in the solid state to give 7. Five-coordinate 7 reacted with H/sub 2/, CO, and C/sub 2/H/sub 4/ in the solid state to form MoH/sub 2/(triphos)(PMe/sub 2/Ph)/sub 2/ (8), Mo(CO)(triphos)(PMe/sub 2/Ph)/sub 2/ (9), and Mo(C/sub 2/H/sub 4/)(triphos)(PMe/sub 2/Ph)/sub 2/ (10), respectively. Reaction of solids 7, 8, and 10 with N/sub 2/ regenerated 1. Structural assignments of the new complexes are based upon /sup 31/P and /sup 1/H NMR spectral data. Triphos is shown to adopt both fac and mer configurations. 33 references, 1 table.
- Research Organization:
- Univ. of Nebraska, Lincoln (USA)
- OSTI ID:
- 5782954
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:17
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
CHEMICAL PREPARATION
AMMONIA
AROMATICS
HYDRAZINE
MOLYBDENUM CHLORIDES
ORGANIC PHOSPHORUS COMPOUNDS
NMR SPECTRA
PHOSPHORUS 31
PROTONS
BARYONS
CHLORIDES
CHLORINE COMPOUNDS
ELEMENTARY PARTICLES
FERMIONS
HADRONS
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MOLYBDENUM COMPOUNDS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUCLEI
NUCLEONS
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS ISOTOPES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
090320* - Inorganic Hydrogen Compound Fuels- Preparation- (1976-1989)
400201 - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation