Low temperature pathways to Chevrel phases via reduced molybdenum sulfide cluster complexes
The initial cluster compound, Na[sub 2y]Mo[sub 6]S[sub 8+y] (py)[sub x], was discovered by reacting Mo[sub 6]Cl[sub 12] with higher stoichiometries of sodium hydrosulfide and sodium butoxide in butanol/pyridine. This compound can subsequently undergo ligand exchange reactions to form a variety of cluster complexes. Single-crystal structure determinations are reported for the pyridine (py), piperidine (pip), and pyrrolidine (pyrr) complexes: triclinic Mo[sub 6]S[sub 8](PY)[sub 6][center dot]1.65py, cubic Mo[sub 6]S[sub 8](py)[sub 6][center dot]2py, Mo[sub 6]S[sub 8](pip)[sub 6][center dot]7pip, and Mo[sub 6]S[sub 8](pyrr)[sub 6][center dot]1pyrr. Delegation of the cluster complexes was explored. Direct heating under dynamic vacuum led to incomplete deligation. Reactions with tin and lead resulted in formation of corresponding Chevrel phase compounds along with MoS[sub 2]. Thermolysis reactions in the presence of flowing ammonia gas resulted in further delegation than was evidenced for reactions explored in vacuo. Solution reactions with strong acids were studied in an attempt to protonate the ligands and thus make them better leaving groups only limited success was achieved. A new preparative route was developed for ternary molybdenum sulfides. Cation exchange reactions with Na[sub 2y]Mo[sub 6]S[sub 8+y](MeOH)[sub x] were used to form the cobalt, tin, lead, and holmium compounds. Preliminary hydrodesulfurization studies on the sodium and cobalt compounds showed that they possess larger surface areas and thiophene conversion percentages than Chevrel phases, but a lower HDS rate.
- Research Organization:
- Ames Lab., IA (United States)
- Sponsoring Organization:
- USDOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6445672
- Report Number(s):
- IS-T-1609; ON: DE93013282
- Resource Relation:
- Other Information: Thesis (Ph.D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
02 PETROLEUM
DESULFURIZATION
CATALYSTS
MOLYBDENUM SULFIDES
COMPLEXES
CRYSTAL STRUCTURE
HETEROGENEOUS CATALYSIS
LIGANDS
MOLECULAR CLUSTERS
PIPERIDINES
POLYCYCLIC SULFUR HETEROCYCLES
PYRIDINE
PYRROLIDINES
AMINES
AZINES
AZOLES
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
HETEROCYCLIC COMPOUNDS
MOLYBDENUM COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PYRIDINES
PYRROLES
REFRACTORY METAL COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
360601* - Other Materials- Preparation & Manufacture
400201 - Chemical & Physicochemical Properties
020400 - Petroleum- Processing