Selective Semihydrogenation of Polarized Alkynes by a Gold Hydride Nanocluster.

The hydridic hydrogen in nanogold catalysts has long been postulated as an important intermediate in hydrogenation reactions, but it has not been directly observed. Here, we report the synthesis of a new undecagold cluster with a bidentate phosphine ligand. The chelating effects of the bidentate ligand result in a more symmetric Au11 core with two labile Cl- ligands that can exchange with BH4-, leading to a novel undecagold hydride cluster. The new hydride cluster is discovered to readily undergo hydroauration reaction with alkynes containing electron-withdrawing groups, forming key gold-alkenyl semihydrogenation intermediates, which can be efficiently and selectively converted to Z-alkenes under acidic conditions. All key reaction intermediates are isolated and characterized, providing atomic-level insights into the active sites and mechanisms of semihydrogenation reactions catalyzed by gold-based nanomaterials. The hydridic hydrogen in the undecagold cluster is found to be the key to prevent over hydrogenation of alkenes to alkanes. The current study provides fundamental insights into hydrogenation chemistry enabled by gold-based nanomaterials and may lead to the development of efficient catalysts for selective semihydrogenation or functionalization of alkynes.

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO2 to CO.

It has been a long-standing challenge to create and identify the active sites of heterogeneous catalysts, because it is difficult to precisely control the interfacial chemistry at the molecular level. Here we report the synthesis and catalysis of a heteroleptic gold trihydride nanocluster, [Au22H3(dppe)3(PPh3)8]3+ [dppe = 1,2-bis(diphenylphosphino)ethane, PPh3 = triphenylphosphine]. The Au22H3 core consists of two Au11 units bonded via six uncoordinated Au sites. The three H atoms bridge the six uncoordinated Au atoms and are found to play a key role in catalyzing electrochemical reduction of CO2 to CO with a 92.7% Faradaic efficiency (FE) at -0.6 V (vs RHE) and high reaction activity (134 A/gAu mass activity). The CO current density and FECO remained nearly constant for the CO2 reduction reaction for more than 10 h, indicating remarkable stability of the Au22H3 catalyst. The Au22H3 catalytic performance is among the best Au-based catalysts reported thus far for electrochemical reduction of CO2. Density functional theory (DFT) calculations suggest that the hydride coordinated Au sites are the active centers, which facilitate the formation of the key *COOH intermediate.

The synthesis and characterization of a new diphosphine-protected gold hydride nanocluster.

Gold is the most inert metal and does not form a bulk hydride. However, gold becomes chemically active in the nanometer scale and gold nanoparticles have been found to exhibit important catalytic properties. Here, we report the synthesis and characterization of a highly stable ligand-protected gold hydride nanocluster, [Au22H3(dppee)7]3+ [dppee = bis(2-diphenylphosphino) ethyl ether]. A synthetic method is developed to obtain high purity samples of the gold trihydride nanocluster with good yields. The properties of the new hydride cluster are characterized with different experimental techniques, as well as theoretical calculations. Solid samples of [Au22H3(dppee)7]3+ are found to be stable under ambient conditions. Both experimental evidence and theoretical evidence suggest that the Au22H3 core of the [Au22H3(dppee)7]3+ hydride nanocluster consists of two Au11 units bonded via two triangular faces, creating six uncoordinated Au sites at the interface. The three H atoms bridge the six uncoordinated Au atoms at the interface. The Au11 unit behaves as an eight-electron trivalent superatom, forming a superatom triple bond (Au11 ≡ Au11) in the [Au22H3(dppee)7]3+ trihydride nanocluster assisted by the three bridging H atoms.

The Synthesis, Bonding, and Transformation of a Ligand-Protected Gold Nanohydride Cluster.

Gold does not react with H2 to form bulk hydrides. Here we report the synthesis and characterization of a gold nanohydride protected by diphosphine ligands, [Au22 H4 (dppo)6 ]2+ [dppo=1,8-bis(diphenylphosphino)octane]. The Au22 core consists of two Au11 units bonded by eight Au atoms not coordinated by the diphosphine ligands. The four H atoms are found to bridge the eight uncoordinated Au atoms at the interface. Each Au11 unit can be viewed as a tetravalent superatom forming four delocalized Au-H-Au bonds, similar to the quadruple bond first discovered in the [Re2 Cl8 ]2- inorganic cluster. The [Au22 H4 (dppo)6 ]2+ nanohydride is found to lose H atoms over an extended time via H evolution (H2 ), proton (H+ ) and hydride (H- ) releases. This complete repertoire of H-related transformations suggests that the [Au22 H4 (dppo)6 ]2+ nanohydride is a versatile model catalyst for understanding the mechanisms of chemical reactions involving hydrogen on the surface of gold nanoparticles.

Halogen effects on the electronic and optical properties of Au13 nanoclusters.

We report an experimental and theoretical investigation of the electronic and optical properties of a series of icosahedral Au13 nanoclusters, protected using different halogen ligands (Cl, Br, and I), as well as 1,2-bis(diphenylphosphino)ethane (dppe) ligands. All three clusters are comprised of the same Au13 kernel with two halogens coordinated to the poles of the icosahedral cluster along with five dppe ligands. UV-vis absorption spectra indicate a systematic red shift from Cl to Br to I, as well as a sudden enhancement of the second excitonic peak for the I-coordinated cluster. Density functional theory (DFT) calculations suggest that all clusters possess a wide HOMO-LUMO energy gap of ∼1.79 eV and are used to assign the first two excitonic bands. Frontier orbital analyses reveal several HOMO → LUMO transitions involving halogen-to-metal charge transfers. For the I-coordinated cluster, more complicated I-to-metal charge transfers give rise to different excitation features observed experimentally. The current findings show that halogen ligands play important roles in the electronic structures of gold clusters and can be utilized to tune the optical properties of the clusters.