Synthesis, structure, and characterization of n-ligated Mo[sub 6]S[sub 8]L[sub 6] cluster complexes. Molecular precursors to Chevrel phases

Journal Article · Wed Apr 27 04:00:00 EDT 1994 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00087a017· OSTI ID:7071408

Hilsenbeck, S J; Young, Jr, V G; McCarley, R E ^[1]

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1. Iowa State Univ., Ames, IA (United States)

A modified method has been developed for the synthesis of the Mo[sub 6]S[sub 8] cluster unit in one step from Mo[sub 6]Cl[sub 12] via reaction with NaSH and NaOBu in refluxing n-BuOH-pyridine. The ligand-deficient Na[sub 2x]Mo[sub 6]S[sub 8+x](py)[sub y] (1) serves as a convenient starting material for the preparation of the amine complexes Mo[sub 6]S[sub 8]L[sub 6], with L = pyridine (2), pyrrolidine (4), and piperidine (5). Although propylamine readily dissolves the ligand-deficient starting material, only amorphous Mo[sub 6]S[sub 8](PrNH[sub 2])[sub 6-x] (3) could be isolated. However, the latter acts as a facile reactant for the preparation of the other complexes by ligand substitution. Crystallographic data for the complexes are as follows: Mo[sub 6]S[sub 8](py)[sub 6][center dot]2py (2), cubic, Pa[bar 3], a = 16.994(2) [angstrom], Z = 4, R = 0.0381, R[sub w] = 0.0351; Mo[sub 6]S[sub 8](pyrr)[sub 6][center dot]pyrr (4), tetragonal, I4[sub 1]/a, a = 29.933(4) [angstrom], c = 23.697(8) [angstrom], Z = 16, R = 0.0675, wR2 = 0.2036; Mo[sub 6]S[sub 8](pip)[sub 6][center dot]7pip, (5), tetragonal, in the IR at 380 [+-] 5 cm[sup [minus]1] and in the Raman at 414 [+-] 4 cm[sup [minus]1], assigned as predominantly Mo-S stretching modes. XP spectra give characteristic binding energies at 227.7 [+-] 0.1 (Mo 3d[sub 5/2]), 230.8 [+-] 0.1 (Mo 3d[sub 3/2]), 225.1 [+-] 0.3 (S 2s), 160.6 [+-] 0.1 (S 2p[sub 3/2]), and 161.8 [+-] 0.1 (S 2p[sub 1/2]) eV. Mo-Mo and Mo-S bond distances show little variation among the complexes, with average values of 2.647 and 2.454 [angstrom], respectively. The average Mo-N bond distance, 2.297 [angstrom], indicates rather weak bonding of these N-donor ligands.

• OSTI ID: 7071408
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 33:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CHALCOGENIDES
CHEMICAL PREPARATION
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
ELECTRON SPECTROSCOPY
LASER SPECTROSCOPY
LATTICE PARAMETERS
MOLYBDENUM COMPLEXES
MOLYBDENUM COMPOUNDS
MOLYBDENUM SULFIDES
PHOTOELECTRON SPECTROSCOPY
RAMAN SPECTROSCOPY
REFRACTORY METAL COMPOUNDS
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
SYNTHESIS
TETRAGONAL LATTICES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY SPECTROSCOPY