Synthesis, characterization, and structure of reduced tungsten chalcogenide cluster complexes

New soluble and weakly-coordinated complexes {dollar}rm Wsb6Ssb8(pip)sb6{dollar} and {dollar}rm Wsb6Ssb8{dollar} (BuNH{dollar}sb2)sb6{dollar} were prepared. A new sodium ternary tungsten sulfide, {dollar}rm Nasb{lcub}2x{rcub}(Wsb6Ssb8)Ssb{lcub}x{rcub}(MeOH)sb{lcub}y{rcub},{dollar} was obtained when acetonitrile was used as the solvent in the sulfidation reaction. Furthermore, the tin compound, {dollar}rm Snsb{lcub}x{rcub}(Wsb6Ssb8)Ssb{lcub}x{rcub}(MeOH)sb{lcub}y{rcub}{dollar} was prepared via ion-exchange. Infrared and XP spectra supported the presence of the {dollar}rm Wsb6Ssb8{dollar} cluster units in these ternary tungsten sulfides. These compounds are the first examples of ternary tungsten sulfides that contain the {dollar}rm Wsb6Ssb8{dollar} cluster unit.; New molecular complexes, {dollar}rm Wsb6Sesb8(py)sb6{dollar} and {dollar}rm Wsb6Sesb8(pip)sb6{dollar} were prepared. Single-crystal structures of {dollar}rm Wsb6Sesb8(py)sb6{lcub}cdot{rcub}6py{dollar} and {dollar}rm Wsb6Sesb8(pip)sb6{lcub}cdot{rcub}8pip{dollar} were determined. The average W-W bond distance of 2.690(2)A in these selenide clusters is slightly longer than that of 2.660(2)A in the sulfide analogues. The average W-Se bond distance is about 2.57 A. The {dollar}rm Wsb6Sesb8{dollar} cluster showed a characteristic {dollar}rm Tsb{lcub}1u{rcub}{dollar} W-Se stretching mode at about 250 {dollar}rm cmsp{lcub}-1{rcub}{dollar}. The observed tungsten binding energy of 30.8 eV {dollar}rm (4fsb{lcub}7/2{rcub}){dollar} from XPS is characteristic of the {dollar}rm Wsb6Sesb8{dollar} cluster unit.; The first examples of molecular telluride complexes, {dollar}rm Wsb6Tesb8Lsb6{dollar} (L = py and pip), and {dollar}rm lbrack Na(py)sb6rbrack sp+lbrack Wsb6Tesb8(py)sb6rbrack sp-{dollar} were discovered. {dollar}rm Wsb6Tesb8(PEtsb3)sb6{dollar} was established by ligand displacement of pyridine in {dollar}rm Wsb6Tesb8(py)sb6.{dollar} The cluster unit, {dollar}rm Wsb6Tesb8,{dollar} showed a characteristic {dollar}rm Tsb{lcub}1u{rcub}{dollar} W-Te stretching mode around 180-200 {dollar}rm cmsp{lcub}-1{rcub}.{dollar} The tungsten binding energy of 30.8 eV {dollar}rm (4fsb{lcub}7/2{rcub}){dollar} for {dollar}rm Wsb6Tesb8Lsb6{dollar} compared favorably with values for the sulfide and selenide analogues. The crystal structures of {dollar}rm Wsb6Tesb8(pip)sb6{lcub}cdot{rcub}6pip, Wsb6Tesb8(PEtsb3)sb6,{dollar} and {dollar}rm lbrack Na(py)sb6rbrack sp+lbrack Wsb6Tesb8(py)sb6rbrack sp-{lcub}cdot{rcub}1py{dollar} were reported. The W-Te bond distances are very close to the W-W bond distances of 2.74 A in these telluride clusters. For the ionic complex, both the distorted tungsten octahedral cluster and the shortening of W-W bond confirmed that it was a {dollar}rm 21esp-{dollar} cluster unit. The unique cationic unit {dollar}rm lbrack Na(py)sb6rbrack sp+{dollar} is the first documented example of a sodium ion octahedrally coordinated with six pyridine molecules.; The first examples of the mixed halide-chalcogenide molecular complexes for the hexatungsten cluster unit, {dollar}rmlbrack Wsb6Sesb{lcub}8-x{rcub}Clsb{lcub}x{rcub}(PEtsb3)sb6rbrack sp+,{dollar} were prepared. Structures for {dollar}rmlbrack Wsb6Sesb7Cl(PEtsb3)sb6rbrack lbrack Cl(CHClsb3)sb6rbrack {dollar} and {dollar}rmlbrack Wsb6Sesb{lcub}6.4{rcub}Clsb{lcub}1.6{rcub}(PEtsb3)sb6rbrack lbrack Cl(CHClsb3)sb6rbrack {dollar} were determined. The bridging chlorine atoms are disordered over all the bridging ligand sites in both structures. In the unique {dollar}rmlbrack Cl(CHClsb3)sb6rbrack sp-{dollar} anion unit, six chloroform solvent molecules are octahedrally coordinated to a chlorine anion through the hydrogen atoms of the chloroform.