Publication | Open Access
Isolation and Structural Elucidation of 15‐Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two‐Electron Copper Superatom
42
Citations
37
References
2020
Year
Highly reactive copper-dihydride clusters, [Cu<sub>15</sub> (H)<sub>2</sub> (S<sub>2</sub> CNR<sub>2</sub> )<sub>6</sub> (C<sub>2</sub> Ph)<sub>6</sub> ](PF<sub>6</sub> ) {R = <sup>n</sup> Bu (1<sub>H</sub> ), <sup>n</sup> Pr (2<sub>H</sub> ), <sup>i</sup> Bu (3<sub>H</sub> )}, are isolated during the reaction of [Cu<sub>28</sub> H<sub>15</sub> {S<sub>2</sub> CN<sup>n</sup> Bu<sub>2</sub> }<sub>12</sub> ](PF<sub>6</sub> ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu<sub>13</sub> (S<sub>2</sub> CNR<sub>2</sub> )<sub>6</sub> (C<sub>2</sub> Ph)<sub>4</sub> ]<sup>+</sup> . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH<sub>3</sub> CN)<sub>4</sub> ](PF<sub>6</sub> ), BH<sub>4</sub><sup>-</sup> and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu<sub>15</sub> (D)<sub>2</sub> (S<sub>2</sub> CNR<sub>2</sub> )<sub>6</sub> (C<sub>2</sub> Ph)<sub>6</sub> ]<sup>+</sup> , and a single-crystal neutron structure of 2<sub>H</sub> . Structural characterization of 1<sub>H</sub> reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH<sub>2</sub> )<sup>-</sup> unit. Reaction of 3<sub>H</sub> with Au(I) salts yields a highly luminescent [AuCu<sub>12</sub> (S<sub>2</sub> CN<sup>i</sup> Bu<sub>2</sub> )<sub>6</sub> (C<sub>2</sub> Ph)<sub>4</sub> ]<sup>+</sup> cluster.
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