Synthesis, characterization, and reactivity of sulfided hexanuclear molybdenum cluster compounds

Technical Report · Fri Sep 21 00:00:00 EDT 1990

DOI:https://doi.org/10.2172/6562551· OSTI ID:6562551

Spink, D

Hexanuclear molybdenum clusters with mixed chloride and sulfide bridging ligands were prepared by reacting {alpha}-MoCl{sub 2} with sodium hydrosulfide in the presence of sodium butoxide. The resulting species, Mo{sub 6}Cl{sub (8-x)}S{sub x}{center dot}npy(x {congruent} 3.6, n {congruent} 4, py = pyridine), was pyrophoric and insoluble. The mixed sulfide chloride cluster species Mo{sub 6}S{sub 4}Cl{sub 4}{center dot}6OPEt{sub 3} and Mo{sub 6}S{sub {approximately}5}Cl{sub {approximately}3}{center dot}6PEt{sub 3} and Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} were isolated and characterized. Phosphorus-31 nuclear magnetic resonance, electron paramagnetic resonance, and UV/visible spectra were obtained for each fraction. The completely sulfided cluster, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3}, was prepared similarly and used in various experiments as a possible precursor to Chevrel phase materials of the type Mo{sub 6}S{sub 8}or M{sub n}Mo{sub 6}S{sub 8}. With the goal of removing all of the triethylphosphine ligands, Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} was reacted with the transition metal carbonyls molybdenum hexacarbonyl and dicobalt octacarbonyl. Reaction on the molecular sulfide cluster with copper(I) chloride in toluene gave a completely insoluble product. The reaction of Mo{sub 6}S{sub 8}{center dot}6PEt{sub 3} with propylene sulfide gave a product whose infrared spectra showed only very weak peaks associated with coordinated triethylphosphine. The elemental analysis of this product fit the formula Mo{sub 6}S{sub 8}{center dot}5SPEt{sub 3}. Reactivity of the outer ligands of the Mo{sub 6}S{sub 8}{center dot}npy and Mo{sub 6}S{sub 8}{center dot}(6{minus}x)PrNH{sub x} clusters were investigated. Crystalline Mo{sub 6}S{sub 8}{center dot}6THT was recovered from the reaction of the n-propylamine derivative with THT. A crystal structure determination was done. 87 refs., 12 fig., 15 tabs.

• Research Organization: Ames Lab., Ames, IA (United States)
• Sponsoring Organization: DOE/ER
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6562551
• Report Number(s): IS-T-1520; ON: DE91000739
• Resource Relation: Other Information: Thesis (Ph.D.)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM CHLORIDES
CHEMICAL PREPARATION
MOLYBDENUM SULFIDES
PHOSPHINE OXIDES
PHOSPHINES
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
INFRARED SPECTRA
LIGANDS
NMR SPECTRA
PHOSPHORUS 31
REACTIVITY
STRUCTURAL MODELS
CHALCOGENIDES
CHLORIDES
CHLORINE COMPOUNDS
DIMENSIONS
HALIDES
HALOGEN COMPOUNDS
ISOTOPES
LENGTH
LIGHT NUCLEI
MOLYBDENUM COMPOUNDS
NUCLEI
ODD-EVEN NUCLEI
OXYGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties