High-yield synthesis of the W{sub 6}S{sub 8} cluster unit as the pyridine complex (W{sub 6}S{sub 8})(py){sub 6} and attempts to prepare tungsten analogues of the Chevrel phases
- Ames Lab., IA (United States)
A convenient high-yield synthesis of W{sub 6}Cl{sub 12} has been devised from the reaction of WCl{sub 4} with iron powder at 500 {degrees}C. Conversion to (W{sub 6}S{sub 8})(py){sub 6}, py = pyridine, is effected in essentially quantitative yield by reaction of W{sub 6}Cl{sub 12} with NaSH and NaO-n Bu in 1:12:6 mol ratio in refluxing pyridine (115 {degrees}C). Black crystals of the insoluble complex (W{sub 6}S{sub 8})(py){sub 6} were grown from pyridine solution in a sealed tube at 200 {degrees}C: triclinic, P1; a = 9.397(2), b = 11.932(3), c = 10.624(2) {angstrom}; {alpha} = 114.28(1), {beta} = 108.88(1), {gamma} = 91.19(2){degrees}; Z = 1; R(R{sub w}) = 0.0267 (0.0359). The average bond distances in the cluster molecules, W-W = 2.6617(2), W-S = 2.458(3), and W-N = 2.255(5) {Angstrom}, are similar to those in Mo{sub 6}S{sub 8}(py){sub 6}. IR spectra show strong bands at 378 cm{sup {minus}1}, attributable to the T{sub lu} W-S stretching modes, and 232 cm{sup {minus}1} of uncertain assignment. Several unsuccessful approaches to deligation of (W{sub 6}S{sub 8})- (py){sub 6}, in efforts to prepare W{sub 6}S{sub 8} and M{sub x}W{sub 6}S{sub 8} analogs of the Chevrel phases, are discussed. Sulfidation of W{sub 6}-Cl{sub 12} with variable ratios of NaSH and NaO-n Bu provided evidence for materials with mixed sulfide-chloride cluster units of average composition [(W{sub 6}Cl{sub 6}S{sub 2})Cl{sub 2}(py){sub 4}]{sup {sm_bullet}}5py and (W{sub 6}Cl{sub 2}S{sub 6}){sub 6}.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 458751
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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