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

Abstract

In this paper, we report a high-yield procedure for the synthesis of isolated W6S8(4-tert-butylpyridine)6 clusters from isolated tungsten chloride clusters. We also show that the 4-tert-butylpyridine ligand can be exchanged with triethylphosphine and piperidine.

A low-temperature phase of bis(tetrabutylammonium) octa-μ3-chlorido-hexachlorido-octahedro-hexatungstate

“…At low temperature, the two independent [(W 6 Cl 8 )Cl 6 ] 2À cluster units (Fig. 1) sit on crystallographic inversion centers and have bond lengths and bond angles comparable to those of previously determined structures (Zietlow, Schaefer et al, 1986;Venkataraman et al, 1999). One hydrocarbon chain of one of the two tetrabutylammonium cations (Fig.…”

“…The structure of the [(W 6 Cl 8 )Cl 6 ] 2À anion was first determined by Zietlow, Schaefer et al (1986) at room temperature. A subsequent structure determination of the same form was published by Venkataraman et al (1999). The tungsten(II) halide clusters have been intensely studied because of their fascinating photochemical and electrochemical properties (Maverick et al, 1983;Nocera & Gray, 1984;Zietlow et al, 1985;Zietlow, Nocera et al, 1986;Jackson et al, 1990;Mussell & Nocera, 1990;Arratia-Pé rez & Herná ndez-Acevedo, 1997;Gray, 2009).…”

“…A search of the Cambridge Structural Database (CSD; Version 5.31; Allen, 2002) revealed that the smaller P2 1 /n unit cell observed for the room-temperature structure is common to a range of tetrabutylammonium salts of metal-halide and metal-chalcogenide cluster dianions. Examples include molybdenum halide clusters (Preetz et al, 1992(Preetz et al, , 1994Kirakci et al, 2005), molybdenum chalcogenide/halide clusters (Ebihara et al, 1992), tungsten halide clusters (Zietlow, Schaefer et al, 1986;Venkataraman et al, 1999) and rhenium chalcogenide/halide clusters (Gabriel et al, 1993;Uriel et al, 1995Uriel et al, , 1996Uriel et al, , 2001). Only two examples were found with the same larger P2 1 /c unit cell as the low-temperature phase of the title compound: the [(Os 2 Re 4 Se 8 )Cl 6 ] 2À dianion structure determined at 153 K by Tulsky & Long (2001) and the [(Re 6 Se 5 -Cl 2 N-TMS)Cl 6 ] 2À (TMS is trimethylsilyl) anion structure determined at room temperature by Uriel et al (1996).…”

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

“…The properties of Mo 6 - † Electronic supplementary information (ESI) available: powder X-ray diffraction patterns of W 6 S 8 (morpholine) 23 and were described previously. 20 The synthesis of KSH was also described previously. 20 All other reagents were of commercial origin.…”

“…20 The synthesis of KSH was also described previously. 20 All other reagents were of commercial origin. Morpholine and aniline were dried with potassium hydroxide, degassed and distilled under reduced pressure.…”