Syntheses, Structures, and Stabilities of [PPh4][WS3(SR)] (R = iBu, iPr, tBu, Benzyl, Allyl) and [PPh4][MoS3(StBu)]

Intermediates in the condensation process of [MS4]2- (M = Mo, W) to polythiometalates, in the presence of alkyl halides, had not been reported prior to our communication of [PPh4][WS3(SEt)] (Boorman, P. M.; Wang, M.; Parvez, M. J. Chem. Soc., Chem. Commun. 1995, 999−1000). We now report the isolation of a range of related compounds, with 1°, 2°, and 3° alkyl thiolate ligands, including one Mo example. [PPh4][WS3(SR)] (R = iBu (1), iPr (2), tBu (3), benzyl (5), allyl (6)) and [PPh4][MoS3(StBu)] (4) have been isolated in fair to good yields from the reaction of [PPh4]2[MS4] with the appropriate alkyl halide in acetonitrile and subjected to analysis by X-ray crystallography. Crystal data are as follows:  for 1, triclinic space group P1 (No. 2), a = 11.0377(6) A, b = 11.1307(5) A, c = 13.6286(7) A, α = 82.941(1)°, β = 84.877(1)°, γ = 60.826(1)°, Z = 2; for 2, monoclinic space group P21/c (No. 14), a = 9.499(6) A, b = 15.913(5) A, c = 18.582(6) A, β = 99.29(4)°, Z = 4; for 3, monoclinic space group P21/n (No....