Synthesis, Structure, and Characterization of N-Ligated W6S8L6 Cluster Complexes

An Improved High Yield Synthesis Procedure and Reactivity of W6S8(4-tert-butylpyridine)6

“…The crystals were grown either by the diffusion of DMSO into a solution of the cluster in benzene or by the slow cooling of a hot solution of the cluster in 4- tert -butylpyridine. The unit cell dimensions obtained from single-crystal X-ray diffraction and 1 H NMR of the cluster were similar to those previously reported . We also obtained two more polymorphs for W 6 S 8 (4- tert -butylpyridine) 6 from these crystallization conditions.…”

“…Piperidine was dried with solid KOH and distilled under reduced pressure; all others were used as received. Tungsten metal and tungsten hexachloride were a generous gift from Osram-Sylvania (Towanda, PA) and were purified according to previously reported procedures . KSH was synthesized according to the literature and was shown to be ≥95% pure by iodimetric titration. , (H 3 O) 2 W 6 Cl 8 i Cl 6 a was synthesized according to a recently reported method with high yields and was converted to (Bu 4 N) 2 W 6 Cl 8 Cl 6 using conditions similar to that reported by McCarley .…”

“…Octahedral clusters of molybdenum that are face-capped by sulfur (Mo 6 S 8 units) form intercluster metal−sulfur interactions in an important class of solid-state compounds called “Chevrel Phases” . These compounds possess exciting electronic properties such as superconductivity and are known to be catalysts in the hydrodesulfurization reaction. − Although the Chevrel phases are generally synthesized using conventional solid-state techniques, in recent years it has been shown that the constituent Mo 6 S 8 clusters can be synthesized as isolated units in solution. , Similar chromium and tungsten chalcogenide cluster units have also been synthesized even though their corresponding Chevrel phases are unknown. − Based on the gamut of properties that the Chevrel phases exhibit, these soluble isolated cluster units offer an opportunity to synthesize new materials from these building blocks.…”

Synthesis, characterization and properties of Mo6S8(4-tert-butylpyridine)6 and related M6S8L6 cluster complexes (M = Mo, W)

“…Although tungsten analogues of the Chevrel phases have never been prepared, molecular W 6 S 8 L 6 clusters are available. [17][18][19] In the pursuit of network structures with W 6 S 8 clusters as building blocks, we developed a high yield synthesis of W 6 S 8 (4-tbp) 6 (4-tbp = 4-tert-butylpyridine) starting from (Bu 4 N) 2 W 6 Cl 8 Cl 6 , 20 a procedure that was modified from McCarley's W 6 S 8 (pyridine) 6 cluster synthetic route. 18 Due to the ease of its preparation on a large scale (10 g) and its amenable properties, W 6 S 8 (4-tbp) 6 has become the key intermediate molecule in our cluster research.…”

Novel octahedral tungsten sulfidocyanide cluster anion [W6S8(CN)6]6–

“…4 The building block of the Chevrel phases is an octahedral molybdenum cluster face-capped by eight chalcogenide atoms (Q). Although no tungsten analogues of the Chevrel phases are known, the molecular tungsten clusters W 6 Q 8 L 6 (L = neutral Lewis base ligand) have been synthesized in solution, [5][6][7][8][9][10] as have the Mo 6 S 8 L 6 clusters. 11,12 Our investigation of W 6 S 8 L 6 clusters, 10,[13][14][15] particularly the finding of strong bonding to the W 6 S 8 cluster by isocyanide, 15 suggested cyanide might also be a good ligand.…”