Dinuclear tungsten(V) and molybdenum(V) compounds containing M/sub 2/S/sub 2/(. mu. -S)/sub 2//sup 2 +/ cores. Synthesis and reactivity of (N(C/sub 2/H/sub 5/)/sub 4/)/sub 2/M/sub 2/S/sub 12/ (M = W or Mo) and the crystal structure of (N(C/sub 2/H/sub 5/)/sub 4/)/sub 2/W/sub 2/S/sub 2/(. mu. -S)/sub 2/(S/sub 4/)/sub 2/
Rational synthesis of dimeric tungsten(V) and molybdenum(V) sulfide complexes having high sulfur-to-metal ratios are described. The M/sub 2/S/sub 12//sup 2 -/ anions (M = W or Mo) have been isolated in high yields as their tetraethylammonium (NEt/sub 4//sup +/) salts from the reactions of elemental sulfur with the corresponding (NH/sub 4/)/sub 2/MS/sub 4/ in hot N,N-dimethylformamide. (NEt/sub 4/)/sub 2/W/sub 2/S/sub 12/ (1) was found by single-crystal X-ray diffraction methods to crystallize from CH/sub 3/CN in the tetragonal space group P4/ncc with a = 21.185 (4) A, c = 15.320 (3) A, and Z = 8. the structure of the W/sub 2/S/sub 12//sup 2 -/ anion consists of a syn-W/sub 2/S/sub 2/(..mu..-S)/sub 2//sup 2 +/ core coordinated by two bidentate tetrasulfido (S/sub 4//sup 2 -/) ligands. An analogous structure (i.e., Mo/sub 2/S/sub 4/(S/sub 4/)/sub 2//sup 2 -/) is indicated for (NEt/sub 4/)/sub 2/Mo/sub 2/S/sub 12/ (2). Both 1 and 2 have been found to be convenient precursors for synthesizing other dimeric compounds. The bis(dithiocarbamate) derivatives. W/sub 2/S/sub 4/(S/sub 2/CNR/sub 2/)/sub 2/, where R = i-C/sub 4/H/sub 9/ (3) or R = C/sub 2/H/sub 5/ (5), have been prepared in good yields from 1, while (NEt/sub 4/)/sub 2/Mo/sub 2/S/sub 4/(S/sub 2/)/sub 2/ and MoS/sub 4/(S/sub 2/CN(i-C/sub 4/H/sub 9/)/sub 2/)/sub 2/ have been synthesized from 2. The tungsten and molybdenum dimers have been characterized by a variety of spectroscopic techniques. 39 references, 1 figure, 5 tables.
- Research Organization:
- Exxon Research and Engineering Co., Annandale, NJ
- OSTI ID:
- 5956797
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:26
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
02 PETROLEUM
MOLYBDENUM COMPLEXES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
SULFIDES
CRYSTAL STRUCTURE
TUNGSTEN COMPLEXES
CHEMICAL REACTION YIELD
DIMERS
EXPERIMENTAL DATA
LATTICE PARAMETERS
SALTS
SPACE GROUPS
X-RAY DIFFRACTION
CHALCOGENIDES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
INFORMATION
NUMERICAL DATA
SCATTERING
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
YIELDS
360602* - Other Materials- Structure & Phase Studies
400201 - Chemical & Physicochemical Properties
020400 - Petroleum- Processing