Zirconium Clusters from the Reaction of ZrCl<sub>4</sub> with HSnBu<sub>3</sub> Followed by Addition of Phosphines:  Zr<sub>6</sub>Cl<sub>14</sub>H<sub>4</sub>(PR<sub>3</sub>)<sub>4</sub> Compounds ChenLinfeng CottonF. Albert WojtczakWilliam A. 1996 The reduction of ZrCl<sub>4</sub> with HSnBu<sub>3</sub> followed by addition of phosphines yields pentanuclear cluster compounds Zr<sub>5</sub>Cl<sub>12</sub>(PR<sub>3</sub>)<sub>5</sub>H<sub>4</sub> (<b>2</b>) and three types of hexanuclear cluster compounds, Zr<sub>6</sub>Cl<sub>14</sub>(PR<sub>3</sub>)<sub>4</sub>H<sub>4</sub> (<b>3</b>), as well as [Zr<sub>6</sub>Cl<sub>18</sub>H<sub>5</sub>]<sup>3-</sup> (<b>4</b>) and a small amount of [Zr<sub>6</sub>Cl<sub>18</sub>H<sub>4</sub>]<sup>4-</sup> (<b>5</b>). Separation of these compounds has been achieved by using different solvents in which they have different solubilities and stabilities. The presence of hydrogen atoms and their numbers have been established by<sup> 1</sup>H NMR spectroscopy. The compounds Zr<sub>6</sub>Cl<sub>14</sub>(PR<sub>3</sub>)<sub>4</sub>H<sub>4</sub> (<b>3a</b>, R = Me; <b>3b</b>, R = Et;<b> 3c</b>, R = <i>n</i>-Pr) and [HP(<i>t</i>-Bu)<sub>2</sub>Ph]<sub>3</sub>[Zr<sub>6</sub>Cl<sub>18</sub>H<sub>5</sub>] (<b>4d</b>) have been characterized by X-ray crystallography. In compounds <b>3a</b> and <b>3b</b>, four hydrogen atoms distributed on the eight triangular faces of the Zr<sub>6</sub> octahedron were located. Compound <b>3a</b>·2CH<sub>2</sub>Cl<sub>2</sub> crystallized in the monoclinic space group <i>P</i>2<sub>1</sub>/<i>n</i> with cell dimensions (−75 °C) of <i>a</i> = 11.149(2) Å, <i>b</i> = 11.049(4) Å, <i>c</i> = 20.666(7) Å, β = 103.42(2)°, <i>V</i> = 2476(1) Å<sup>3</sup>, and <i>Z</i> = 2. Compound<b> 3b</b>·2CH<sub>2</sub>Cl<sub>2</sub> crystallized in orthorhombic space group <i>Pbca</i> with cell dimensions (−60 °C) of <i>a</i> = 12.127(3) Å, <i>b</i> = 21.793(5) Å, <i>c</i> = 23.022(4) Å, <i>V</i> = 6084(2) Å<sup>3</sup>, and <i>Z</i> = 4. Compound<b> 3c</b>·2.31C<sub>6</sub>H<sub>6</sub> crystallized in triclinic space group <i>P</i>1̄ with cell dimensions (−60 °C) of <i>a</i> = 12.585(1) Å, <i>b</i> = 13.679(2) Å, <i>c</i> = 23.319(4) Å, α = 97.08(2)°, β = 94.77(2)°, γ = 93.30(2)°, <i>V</i> = 3960.6(9) Å<sup>3</sup>, and <i>Z</i> = 2. Compound <b>4d</b>·2CH<sub>2</sub>Cl<sub>2</sub>·2C<sub>6</sub>H<sub>6</sub> crystallized in monoclinic space group <i>C</i>2/<i>c</i> with cell dimensions (−60 °C) of <i>a</i> = 29.432(4) Å, <i>b</i> = 13.503(1) Å, <i>c</i> = 23.892(3) Å, β = 110.96(1)°, <i>V</i> = 8867(2) Å<sup>3</sup>, and <i>Z</i> = 4. In compounds <b>3a</b>−<b>c</b>, six zirconium atoms are arranged in a slightly elongated octahedron with four phosphine ligands at the equatorial positions. The distance of Zr<sub>eq</sub>−Zr<sub>ax</sub> (3.359(8) Å) is slightly longer that of Zr<sub>eq</sub>−Zr<sub>eq</sub> (3.308(6) Å), but both of them are shorter than that found in compound <b>4d</b> (3.416(2) Å).