Synthesis, structure, and characterization of N-ligated W{sub 6}S{sub 8}L{sub 6} cluster complexes
- Cornell Univ., Ithaca, NY (United States)
- Princeton Univ., NJ (United States)
- NEC Research Inst., Princeton, NJ (United States)
The synthesis and structure determination of two N-ligated W{sub 6}S{sub 8}(C{sub 5}H{sub 5}N){sub 6} (1) from the reaction of W{sub 6}Cl{sub 12}, NaSH, and NaOBu in refluxing pyridine and the preparation of W{sub 6}S{sub 8}(C{sub 9}H{sub 13}N){sub 6}{center_dot}6C{sub 6}H{sub 6}(2) from the reaction of W{sub 6}Cl{sub 12}, KSH, KOBu, and 4-tert-butylpyridine in DMF (followed by recrystallization from benzene). Thin, orange plate-shaped crystals of W{sub 6}S{sub 8}(C{sub 5}H{sub 5}N){sub 6} (1) were isolated after working up the product from the above reaction in pyridine at 210 {degrees}C. They crystallize in the space group P1 (No. 2) with lattice constants a=9.404(2) {Angstrom}, b = 10.725(5) {Angstrom}, c = 11.905(6) {Angstrom}, a = 114.43(3){degrees}, {beta}=90.52(3){degrees}, {gamma}=109.07(3){degrees}, V = 1018.6(7) {Angstrom}, and Z = 1, with R(R{sub w})=0.0525(0.0686). Large, dark red-brown crystals of W{sub 6}S{sub 8}(C{sub 9}H{sub 13}N){sub 6}{center_dot}6C{sub 6}H{sub 6} (2) were prepared by a method similar to that for 1, but under less rigorous conditions. This method leads to the isolation of W{sub 6}S{sub 8}(C{sub 9}H{sub 13}N){sub 6}{center_dot}6C{sub 6}H{sub 6}(2), which crystallizes in the space group R3 (No. 148) with lattice constants a = 20.208(3) {Angstrom}, c = 20.843(3) {Angstrom}, V=7371(2) {Angstrom}{sup 3}, and Z=3, with R(R{sub w})=0.0413 (0.0482). Both 1 and 2 contain the neutral, substitution-resistant W{sub 6}S{sub 8} cluster core consisting of an octahedral arrangement of tungsten atoms with face-capping sulfur atoms. The coordination environment of each tungsten atom is completed by a single pyridine (or 4-tert-butylpyridine) ligand in the exo position. All of the W-W and W-S distances in these clusters fall within the ranges 2.652-2.667 {Angstrom} (for W-W) and 2.430-2.478 {Angstrom} (for W-S), which are comparable to those found in related tungsten sulfide cluster complexes.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-87ER45298
- OSTI ID:
- 508708
- Journal Information:
- Inorganic Chemistry, Vol. 34, Issue 17; Other Information: PBD: 16 Aug 1995
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis, structure, and characterization of n-ligated Mo[sub 6]S[sub 8]L[sub 6] cluster complexes. Molecular precursors to Chevrel phases
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