Synthesis and characterization of tetranuclear molybdenum(II) cluster derivatives

Technical Report · Sun Nov 01 04:00:00 EST 1987

OSTI ID:6360955

Vogel, E A.F.

A series of new tetranuclear molybdenum(II) nitrile cluster derivatives is reported. Improvements in the synthetic routes to these and other derivatives is also reported. The single crystal x-ray structure of Mo/sub 4/Cl/sub 12//sup 4/minus// is modeled. New tetrameric nitrile derivatives with the stoichiometry Mo/sub 4/Cl/sub 8/(RCN)/sub 4/ (R = Pr/sup n/, Pr/sup i/, Bu/sup t/, PhCH/sub 2/) have been isolated by ligand exchange from Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/ and/or direct synthesis from Mo/sub 4/Cl/sub 8/(PBu/sup n/sub 3//)/sub 4/. Mo/sub 4/Cl/sub 8/(Pr/sup n/CN)/sub 4/ was synthesized with higher yields and with simpler reaction conditions than Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/. Improved synthetic routes for R/sub 4/Mo/sub 4/Cl/sub 12/ (R = Et/sub 4/N, Pr/sub 4/N) have been developed. (Et/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ can be directly synthesized from the phosphine tetramer, circumventing the preparation of the reactive species-Mo/sub 4/Cl/sub 8/(EtCN)/sub 4/, which is the most difficult precursor to prepare. A change in reaction solvent, from dichloromethane or dichloroethane to chlorobenzene, in the preparation of (Pr/sub 4/N)/sub 4/Mo/sub 4/Cl/sub 12/ has permitted its isolation under less rigorous conditions and in high yield. A single crystal structure determination has been done on a sample of (Ph/sub 4/P)/sub 4/Mo/sub 4/Cl/sub 12/. Although, the quality of the data is poor, the structure of the Mo/sub 4/Cl/sub 12/ cluster core was refined. Four complex types have been found to fit the data. 22 refs., 12 figs., 7 tabs.

• Research Organization: Ames Lab., IA (USA)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6360955
• Report Number(s): IS-T-1331; ON: DE89007621
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360601 -- Other Materials-- Preparation & Manufacture
360602* -- Other Materials-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
BOND ANGLE
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
CRYSTAL STRUCTURE
DERIVATIZATION
DISTANCE
HALIDES
HALOGEN COMPOUNDS
INFRARED SPECTRA
INTERATOMIC DISTANCES
LATTICE PARAMETERS
LIGANDS
MOLECULAR STRUCTURE
MOLYBDENUM CHLORIDES
MOLYBDENUM COMPOUNDS
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS