Synthesis and structure of two octahedral molybdenum chloride sulfide clusters
A preparation for chloride sulfide Mo/sub 6/X/sub 8/ clusters has been devised which employs substitution by sulfide into the Mo/sub 6/Cl/sub 8//sup 4 +/ cluster. The Mo/sub 6/Cl/sub 7/S/sup 3 +/ cluster has been isolated in the two compounds (C/sub 5/H/sub 5/NH)/sub 3/((Mo/sub 6/Cl/sub 7/S)Cl/sub 6/) x 3(C/sub 5/H/sub 5/NH)Cl and (C/sub 5/H/sub 5/NH)/sub 3/((Mo/sub 6/Cl/sub 7/S)Cl/sub 6/). The structures of both compounds were determined by single crystal x-ray techniques. Despite the different site symmetries of the (Mo/sub 6/Cl/sub 7/S)Cl/sub 6//sup 3 -/ units in the two compounds (S/sub 6/ in the former, C/sub i/ in the latter), corresponding average bond distances and angles are equivalent. The infrared spectra (200 to 450 cm/sup -1/) of the two compounds are identical, and exhibit a band at 421 cm/sup -1/ assigned to a (Mo/sub 6/Cl/sub 7/S)Cl/sub 6//sup 3 -/ cluster vibration of predominant Mo-S character. Resolution of the chlorine 2p photoelectron spectra into components reveals not only that sulfide occupies a bridging ligand site of the (Mo/sub 6/Cl/sub 7/S)Cl/sub 6//sup 3 -/ cluster, but also that the difference between the chlorine 2p binding energies of the bridging and terminal chlorides is anomalously small. The Mo/sub 6/S/sub 6/Cl/sub 2/ cluster has been isolated in the novel compound (Mo/sub 6/S/sub 6/Cl/sub 2/)(NC/sub 5/H/sub 5/)/sub 6/. The structure, determined by single crystal x-ray techniques, consists of an approximately cubic Mo/sub 6/X/sub 8/ cluster with six terminal pyridine ligands. (Mo/sub 6/S/sub 6/Cl/sub 2/)(NC/sub 5/H/sub 5/)/sub 6/ is the first example of a Mo/sub 6/X/sub 8/ cluster with terminal ligands which has fewer that 24 electrons in its metal-metal bonding orbitals. X-ray powder data indicates this compound may be one composition in a molecular solid solution (Mo/sub 6/S/sub 7-x/Cl/sub 1+x/)(NC/sub 5/H/sub 5/)/sub 6/(0 less than or equal to x less than or equal to 2).
- Research Organization:
- Ames Lab., IA (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5508179
- Report Number(s):
- IS-T-881
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
AMINES
AMMONIUM COMPOUNDS
AZINES
CHALCOGENIDES
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFRARED SPECTRA
MOLECULAR STRUCTURE
MOLYBDENUM CHLORIDES
MOLYBDENUM COMPLEXES
MOLYBDENUM COMPOUNDS
MOLYBDENUM SULFIDES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
PYRIDINIUM COMPOUNDS
QUATERNARY COMPOUNDS
SCATTERING
SPECTRA
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION