Reactions of tetrathiotungstate and tetrathiomolybdate with substituted haloalkanes

Reactions of [PPh4](2) [WS4] in CH3CN with excess n-hexylbromide, 1,4-dichlorobutane, 2-( bromomethyl) tetrahydro-2H-pyran) (bmthp), and 2-( bromoethyl)-1,3-dioxane (bedo) followed by extraction with THF afforded a series of alkylthiolatotrithiotungstate complexes, [PPh4][(RS) WS3] (1: R = n-hexyl; 2: R = ClCH2CH2CH2CH2; 3: R = mthp; 4: R = edo), and the analogous reactions of [PPh4](2) [MoS4] in CH3CN-THF with excess bmthp and bedo also generated [PPh4][(RS) MoS3] (5: R = mthp; 6: R = edo), albeit in low yields. Treatment of [PPh4](2) [WS4] in CH3CN with excess (S)-(+)- 3-bromo-2-methyl-1-propanol turned out to give a trinuclear, [PPh4](2) [W3S8 ((S)-(+)- OCH2CH(Me) CH2Br)(2)] (7). Compounds 1-7 were characterized spectroscopically and the crystal structures of 2- 7 were determined by X-ray analysis. All the mononuclear complexes 2- 6 assume tetrahedral structures, being coordinated by one thiolate sulfur and three terminal sulfido ligands, and no additional coordination was observed by the O-donor portions of mthp or edo. The structure of 7 consists of a linear W-3 spine and two (S)-(+)- OCH2CH(Me) CH2Br ligands are coordinated at the central W atom.