Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Bonding and Acidity of the Formal Hydride in the Prototypical Au 9 (PPh 3 ) 8 H 2+ Nanocluster

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry Stony Brook University 100 Nicolls Rd. Stony Brook NY 11794 USA
  2. Department of Chemistry Brandeis University 415 South St. Waltham MA 02453 USA
+ Show Author Affiliations

Abstract The role of hydrogen atoms as surface ligands on metal nanoclusters is of profound importance but remains difficult to directly study. While hydrogen atoms often appear to be incorporated formally as hydrides, evidence suggests that they donate electrons to the cluster's delocalized superatomic orbitals and may consequently behave as acidic protons that play key roles in synthetic or catalytic mechanisms. Here we directly test this assertion for the prototypical Au 9 (PPh 3 ) 8 H 2+ nanocluster, formed by addition of a hydride to the well‐characterized Au 9 (PPh 3 ) 8 3+ . Using gas‐phase infrared spectroscopy, we were able to unambiguously isolate Au 9 (PPh 3 ) 8 H 2+ and Au 9 (PPh 3 ) 8 D 2+ , revealing an Au−H stretching mode at 1528 cm −1 that shifts to 1038 cm −1 upon deuteration. This shift is greater than the maximum expected for a typical harmonic potential, suggesting a potential governing cluster‐H bonding that has some square‐well character consistent with the hydrogen nucleus behaving as a metal atom in the cluster core. Complexing this cluster with very weak bases reveals a redshift of 37 cm −1 in the Au−H vibration, consistent with those typically seen for moderately acidic groups in gas phase molecules and providing an estimate of the acidity of Au 9 (PPh 3 ) 8 H 2+ , at least with regard to its surface reactivity.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0021991
OSTI ID:
1991441
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 35 Vol. 135; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (33)

Photovoltaic Properties of Glutathione-Protected Gold Clusters Adsorbed on TiO 2 Electrodes journal June 2010
Oxygen Electroreduction Catalyzed by Gold Nanoclusters: Strong Core Size Effects journal June 2009
The Synthesis, Bonding, and Transformation of a Ligand‐Protected Gold Nanohydride Cluster journal November 2020
Crystal Structure, Electrochemical and Optical Properties of [Au9(PPh3)8](NO3)3 journal January 2008
Optimized Slater-type basis sets for the elements 1-118 journal May 2003
Vibrational spectroscopy of the cryogenically cooled O- and N-protomers of 4-aminobenzoic acid: Tag effects, isotopic labels, and identification of the E,Z isomer of the O-protomer journal November 2020
Fluorescent Gold Nanoclusters: Recent Advances in Sensing and Imaging journal October 2014
Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities journal September 2016
Benchmark Study of Density Functional Theory for Neutral Gold Clusters, Aun (n = 2–8) journal March 2017
Blue- and Red-Shifting Hydrogen Bonding: A Gas Phase FTIR and Ab Initio Study of RR′CO···DCCl3 and RR′S···DCCl3 Complexes journal April 2018
Light Exposure Promotes Degradation of Intermediates and Growth of Phosphine-Ligated Gold Clusters journal January 2020
Ion Mobility Spectrometry Characterization of the Intermediate Hydrogen-Containing Gold Cluster Au7(PPh3)7H52+ journal March 2021
Atomically Precise Gold Nanoclusters as New Model Catalysts journal March 2013
Generation of Singlet Oxygen by Photoexcited Au 25 (SR) 18 Clusters journal April 2014
Anomalous Behavior of Atomic Hydrogen Interacting with Gold Clusters journal November 2003
Red-, Blue-, or No-Shift in Hydrogen Bonds:  A Unified Explanation journal April 2007
Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster and Optical Properties
  • Zhu, Manzhou; Aikens, Christine M.; Hollander, Frederick J.
  • Journal of the American Chemical Society, Vol. 130, Issue 18, p. 5883-5885 https://doi.org/10.1021/ja801173r
journal May 2008
N-Heterocyclic Carbene-Stabilized Hydrido Au24 Nanoclusters: Synthesis, Structure, and Electrocatalytic Reduction of CO2 journal May 2022
Selective Semihydrogenation of Polarized Alkynes by a Gold Hydride Nanocluster journal June 2022
Hydride-Doped Gold Superatom (Au 9 H) 2+ : Synthesis, Structure, and Transformation journal June 2018
Infrared Spectra and DFT Calculations for the Gold Hydrides AuH, (H 2 )AuH, and the AuH 3 Transition State Stabilized in (H 2 )AuH 3 journal March 2002
Characterization of Gallosilicate MFI-Type Zeolites by IR Spectroscopy of Adsorbed Probe Molecules journal April 1996
Gold(I) Hydride Intermediate in Catalysis: Dehydrogenative Alcohol Silylation Catalyzed by Gold(I) Complex journal August 2009
Hydride, chloride, and bromide show similar electronic effects in the Au 9 (PPh 3 ) 8 3+ nanocluster journal January 2020
Hydride- and halide-substituted Au9(PH3)83+ nanoclusters: similar absorption spectra disguise distinct geometries and electronic structures journal January 2021
Infrared photodissociation spectroscopy of H+(H2O)6·Mm (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O+ and H5O2+ core isomers journal January 2011
The zero‐order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules journal October 1996
Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update journal May 1998
A unified view of ligand-protected gold clusters as superatom complexes journal July 2008
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry journal July 2009
Ligand effects in catalysis by atomically precise gold nanoclusters journal October 2017
Unraveling the long-pursued Au 144 structure by x-ray crystallography journal October 2018
Quantum Structure of the Intermolecular Proton Bond journal April 2007

Similar Records

Related Subjects