Synthesis, characterization, and substitution chemistry of [Bu4N](2)[W6Cl8(OSO2CF3)(6)]. A versatile precursor for axially substituted clusters containing the {W6Cl8}(4+) core

The new cluster [Bu4N](2)[W6Cl8(OSO2CF3)(6)] (1) has been prepared and stru cturally characterized This material is an effective precursor for the gene ration of cluster ions with the general formula [W6Cl8L6](n) (L = Cl-, Br-, I-, NCS-, NCO-, NCSe-, and O=PPh3; n = 2- or 4+). The last three clusters are new. The products have been characterized by LR spectroscopy, NMR spect roscopy, and FAB mass spectrometry. In addition to 1, the products [BU4N](2 )[W6Cl8(NCS)(6)] (5) and [Bu4N](2)[W6Cl8(NCO)(6)] (7) were structurally cha racterized. Crystal data for 1: space group, P2(1/C) (No. 14); a 11.116(5) Angstrom; b = 27.952(1) Angstrom; c = 24.516(1) Angstrom; beta = 95.182(9)d egrees; V = 7586.3(5) Angstrom(3); Z = 4. Crystal data for 5: space group, P2(1)/n (No. 14); a = 11.3323(9) Angstrom; b = 12.3404(9) Angstrom; c = 44. 583(3) Angstrom; beta = 97.089(1)degrees; V = 6187.1(7) Angstrom(3); Z = 4. Crystal data for 7: space group, P1 (No. 2); a = 11.8009(8) Angstrom; b = 11.9332(8) Angstrom; c = 11.9522(8) Angstrom; alpha = 77.904(1)degrees; bet a = 95.182(9)degrees; gamma = 62.574(1)degrees; V = 1450.5(2) Angstrom(3); Z = 1.