Low temperature pathways to Chevrel phases via reduced molybdenum sulfide cluster complexes

Technical Report · Tue Mar 30 04:00:00 EST 1993

OSTI ID:6445672

Shane, H

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: DOE; USDOE, Washington, DC (United States)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6445672
• Report Number(s): IS-T-1609; ON: DE93013282
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400 -- Petroleum-- Processing
36 MATERIALS SCIENCE
360601* -- Other Materials-- Preparation & Manufacture
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
AMINES
AZINES
AZOLES
CATALYSIS
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DESULFURIZATION
HETEROCYCLIC COMPOUNDS
HETEROGENEOUS CATALYSIS
LIGANDS
MOLECULAR CLUSTERS
MOLYBDENUM COMPOUNDS
MOLYBDENUM SULFIDES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PIPERIDINES
POLYCYCLIC SULFUR HETEROCYCLES
PYRIDINE
PYRIDINES
PYRROLES
PYRROLIDINES
REFRACTORY METAL COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS