Preparation and substitution chemistry of [Bu4N](2)[W6Cl8(p-OSO2C6H4CH3)(6)]. A useful precursor for pseudohalide, acetate, and organometallic complexes containing the {W(6)Cl8}(4+) core

The tosylate (p-toluenesulfonate) cluster [Bu4N](2)[W6Cl8(p-OSO2C6H4CH3)(6) ] (1) has been prepared and characterized by IR and NMR spectroscopy, eleme ntal analysis, and an X-ray crystal structure. This cluster complex is show n to be a useful starting material for the preparation of pseudohalide clus ters, [Bu4N](2)[W6Cl8(NCQ)(6)] (Q = O (2), S (3), and Se (4)), in high yiel ds. Cluster I also serves as a precursor to the new cluster commpounds: [Bu 4N](2)[W6Cl8(O2CCH3)(6)] (5), [Bu4N](2)[W6Cl8{(mu -NC)Mn(CO)(2)(C5H5)}(6)] (6), [W6Cl8{(mu -NC)Ru(PPh3)(2)(C5H5)}(6)][ p-OSO2C6H4CH3](4) (7), and [W6C l8{(mu -NC)Os(PPh3)(2)(C5H5)}(6)][ p-OSO2C6H4CH3](4) (8). X-ray crystal str uctures are reported for 1, 4, and 5.