Reactions of tetrathiotungstate and tetrathiomolybdate with substituted haloalkanes

摘要

Reactions of [PPh_4]_2[WS_4] in CH_3CN 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, [PPh_4][(RS)WS_3] (1: R = n-hexyl; 2: R = ClCH_2CH_2CH_2; 3: R = mthp; 4: R = edo), and the analogous reactions of [PPh_4]_2[MoS_4] in CH_3CN-THF with excess bmthp and bedo also generated [PPh_4][(RS)MoS_3] (5: R = mthp; 6; R =edo), albeit in low yields. Treatment of [PPh_4]_2[WS_4] in CH_3CN with excess (S)-(+)-3-bromo-2-methyl-1-propanol turned out to give a trinuclear, [PPh_4]_2[W_3S_8((S)-(+)-OCH_2CH(Me)CH_2bR)_2] (7). Compounds 1-7 were characterized spectroscopillary 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)-(+)-OCH_2CH(Me)CH_2Br ligands are coordinated at the central W atom.