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

Small. 2021 Jul;17(27):e2002544. doi: 10.1002/smll.202002544. Epub 2020 Oct 28.

Abstract

Highly reactive copper-dihydride clusters, [Cu15 (H)2 (S2 CNR2 )6 (C2 Ph)6 ](PF6 ) {R = n Bu (1H ), n Pr (2H ), i Bu (3H )}, are isolated during the reaction of [Cu28 H15 {S2 CNn Bu2 }12 ](PF6 ) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu13 (S2 CNR2 )6 (C2 Ph)4 ]+ . Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH3 CN)4 ](PF6 ), BH4- and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu15 (D)2 (S2 CNR2 )6 (C2 Ph)6 ]+ , and a single-crystal neutron structure of 2H . Structural characterization of 1H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH2 )- unit. Reaction of 3H with Au(I) salts yields a highly luminescent [AuCu12 (S2 CNi Bu2 )6 (C2 Ph)4 ]+ cluster.

Keywords: copper; hydride; nanoclusters; neutron diffraction.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Copper*
  • Crystallography, X-Ray
  • Electrons*

Substances

  • Copper