Isolation and Structural Elucidation of 15‐Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two‐Electron Copper Superatom

Highly reactive copper‐dihydride clusters, [Cu 15 (H) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ](PF 6 ) {R  = n Bu ( 1 H ), n Pr ( 2 H ), i Bu ( 3 H )}, are isolated during the reaction of [Cu 28 H 15 {S 2 CN n Bu 2 } 12 ](PF 6 ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two‐electron superatom [Cu 13 (S 2 CNR 2 ) 6 (C 2 Ph) 4 ] + . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH 3 CN) 4 ](PF 6 ), BH 4 − and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu 15 (D) 2 (S 2 CNR 2 ) 6 (C 2 Ph) 6 ] + , and a single‐crystal neutron structure of 2 H . Structural characterization of 1 H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH 2 ) − unit. Reaction of 3 H with Au(I) salts yields a highly luminescent [AuCu 12 (S 2 CN i Bu 2 ) 6 (C 2 Ph) 4 ] + cluster.