Sulfur-substituted derivatives of the octa-. mu. /sub 3/-chloro-hexamolybdenum(4+) cluster unit. Synthesis and structure of two salts containing the hexachlorohepta-. mu. /sub 3/-chloro-. mu. /sub 3/-sulfido-hexamolybdenum(3-) anion
A synthetic procedure has been devised for stepwise displacement of chloride by sulfide in the Mo/sub 6/Cl/sub 8//sup 4 +/ cluster via reaction of Mo/sub 6/Cl/sub 12/ with NaSH in refluxing pyridine. The (Mo/sub 6/Cl/sub 7/S)/sup 3 +/ cluster has been isolated in two different salts containing the chloro anion ((Mo/sub 6/Cl/sub 7/S)Cl/sub 6/)/sup 3 -/, and the structures have been determined by x-ray diffraction. (C/sub 5/H/sub 5/NH)/sub 3/((Mo/sub 6/Cl/sub 7/S)Cl/sub 6/) (I) crystallizes in the space group P2/sub 1//c with a = 13.469 (4) A, b = 15.329 (3) A, c = 17.115 (5) A, ..beta.. = 107.19 (3)/sup 0/, and Z = 4. With excess pyridinium ion present in solution, the cubic double salt (C/sub 5/H/sub 5/NH)/sub 3/((Mo/sub 6/Cl/sub 7/S)Cl/sub 6/).3(C/sub 5/H/sub 5/NH)Cl (II) is obtained: space group Pa3, with a = 17.158 (2) A and Z = 4. Bond distances obtained after refinement of the two structures indicate sulfide is probably disordered over only two bridging ligand sites in I but over all eight sites in II. Corresponding average bond distances and angles in the two structures are in close agreement. Similarly, infrared spectra for I and II are in good agreement; a band appearing at 423 cm/sup -1/ is assigned to a vibration of predominant Mo-S character. Chlorine 2p photoelectron spectra were resolved into components giving binding energies for bridging, terminal, and ionic chloride in the structures. Relative areas of the component peaks confirm that sulfide must occupy a bridging ligand position in the (Mo/sub 6/Cl/sub 7/S)/sup 3 +/ cluster.
- Research Organization:
- Ames Lab., IA
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5262116
- Journal Information:
- Inorg. Chem.; (United States), Vol. 21:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM CHLORIDES
CHEMICAL REACTIONS
MOLYBDENUM COMPLEXES
CRYSTAL STRUCTURE
LATTICE PARAMETERS
MOLECULAR STRUCTURE
SYNTHESIS
PYRIDINE
PYRIDINIUM COMPOUNDS
SODIUM SULFIDES
BOND ANGLE
BOND LENGTHS
EXPERIMENTAL DATA
INFRARED SPECTRA
ORGANIC CHLORINE COMPOUNDS
ORGANIC SULFUR COMPOUNDS
X-RAY DIFFRACTION
ALKALI METAL COMPOUNDS
AMINES
AMMONIUM COMPOUNDS
AZINES
CHALCOGENIDES
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LENGTH
MOLYBDENUM COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
QUATERNARY COMPOUNDS
SCATTERING
SODIUM COMPOUNDS
SPECTRA
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)