Synthesis and Structural Characterization of Group 4 Metal Complexes Bearing Pentavalent Phosphorus-Bridged Ligands [(C<sub>13</sub>H<sub>8</sub>)(<sup><i>i</i></sup>Pr<sub>2</sub>N)P(−O)(C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)]<sup>2−</sup> and [(C<sub>13</sub>H<sub>9</sub>)(<sup><i>i</i></sup>
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Treatment of (C13H9)(iPr2N)PCl with Li2C2B10H10 gave, after neutralization with Me3NHCl, a trivalent phosphorus-bridged compound, (C13H9)(iPr2N)P(C2B10H11). It was easily converted to a pentavalent phosphorus-bridged ligand, (C13H9)(iPr2N)P(O)(C2B10H11) (4), by reacting with excess hydrogen peroxide in toluene. An equimolar reaction of 4 with Zr(NMe2)4 in toluene at room temperature afforded a zirconium amide incorporating a fluorenylide unit, [σ:σ-(C13H8)(iPr2N)P(-O)(C2B10H10)]Zr(NMe2)2(THF) (5). Complex 5 was converted to the zirconacarborane [η1:η5-(C13H9)(iPr2N)P(O)(C2B9H10)]Zr(NMe2)2 (6) in refluxing toluene in the presence of Me2NH. Its titanium analogue, [η1:η5-(C13H9)(iPr2N)P(O)(C2B9H10)]Ti(NMe2)2 (7), was directly prepared from the reaction of 4 with Ti(NMe2)4 in refluxing toluene. Complex 7 reacted with KH in C6D6 to generate the deprotonated product {[η1:η5-(C13H8)(iPr2N)P(O)(C2B9H10)]Ti(NMe2)2}{(η6-C6D6)2K} (8). These new complexes were fully characterized by various spectroscopic techniques, elemental analyses, and single-crystal X-ray diffraction studies.
