[Bi<sub>12</sub>Ni<sub>7</sub>(CO)<sub>4</sub>]<sup>4–</sup>: Aggregation of Intermetalloid Clusters by Their
Thermal Deligation and Oxidation
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Abstract
Reported
are the synthesis and structure of the anionic intermetalloid cluster
[Bi<sub>12</sub>Ni<sub>7</sub>(CO)<sub>4</sub>]<sup>4–</sup>. It was synthesized from the known smaller clusters Bi<sub>3</sub>Ni<sub>4</sub>(CO)<sub>6</sub><sup>3–</sup>, Bi<sub>3</sub>Ni<sub>6</sub>(CO)<sub>9</sub><sup>3–</sup>, and Ni@Bi<sub>6</sub>Ni<sub>6</sub>(CO)<sub>8</sub><sup>4–</sup> by their
aggregation as a result of thermal deligation and oxidation. The new
cluster is structurally characterized by single-crystal X-ray diffraction
in the compound (K[crypt])<sub>4</sub>[Bi<sub>12</sub>Ni<sub>7</sub>(CO)<sub>4</sub>] (<b>1</b>), and its presence in solution
is confirmed by electrospray mass spectrometry. It can be viewed as
composed of a Ni-centered icosahedral core of Bi<sub>6</sub>Ni<sub>6</sub>(CO)<sub>4</sub> where two diametrically opposed Ni atoms
are capped by Bi<sub>3</sub> triangles. However, its electron count
is rationalized based on a structure made of fused tetrahedra