Studies of molybdenum-molybdenum bonded species. 1. Synthesis and characterization of a reduction product of Cs/sub 3/Mo/sub 2/Cl/sub 8/H. 2. Mixed sulfur/chlorine-substituted hexanuclear molybdenum clusters
A black powder isolated from the reaction of Cs/sub 3/Mo/sub 2/Cl/sub 8/H and zinc in refluxing pyridine, Mo/sub 1/ /sub 0/Cl/sub 1/ /sub 1/py/sub 0/ /sub 8/, has been studied. The material is amorphous to x-rays, and the infrared spectrum indicates coordinated pyridine and chlorine. The x-ray photoelectron spectrum indicates one type of molybdenum and shows both terminal and bridging chlorine are present in the ratio of 1.5:1.0. Mo/sub 1/ /sub 0/Cl/sub 1/ /sub 1/py/sub 0/ /sub 8/ is stable at elevated temperatures and can be heated in vacuo for over 24 hours at 300/sup 0/C with little change in composition. The best description of this material seems to be a highly bridged, metal-metal bonded cluster or polymer. Mo/sub 6/Cl/sub 12/ has been reacted with various sulfur-containing reagents to prepare mixed chlorine sulfide Mo/sub 6/X/sub 8/ clusters. These clusters have been characterized by x-ray powder diffraction, x-ray photoelectron spectroscopy, and infrared spectroscopy. High reaction temperatures (> 200/sup 0/C) with high ratios of NaSH to Mo/sub 6/Cl/sub 12/ (16:1) result in decomposition of the No/sub 6/X/sub 8/ cluster. Reactions of 1 equivalent of Mo/sub 6/Cl/sub 12/ and 8 equivalents of NaSH at 115/sup 0/C yield amorphous products. Intermediate conditions produce crystalline Mo/sub 6/X/sub 8/ derivatives. These products appear to be solid solutions, or have some amorphous impurity present. A FORTRAN IV computer program for analyzing x-ray photoelectron spectra is described. The program smooths the data, makes baseline and scattering corrections, and fits the corrected spectra with linear combinations of Gaussian and Cauchy functions. The results are useful in inferring structural information. 19 figures, 4 tables.
- Research Organization:
- Ames Lab., IA (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 6654677
- Report Number(s):
- IS-T-959; ON: DE83004971
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPLEXES
AZINES
CESIUM COMPLEXES
CHALCOGENIDES
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
COMPUTER CALCULATIONS
DATA
DIFFRACTION
ELECTRON SPECTROSCOPY
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PYRIDINES
REDUCTION
SCATTERING
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION