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Title: Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C5SC03568F· OSTI ID:1239322
 [1];  [2];  [3];  [3];  [3];  [3];  [3];  [4];  [5];  [1];  [3];  [1]
  1. Tsinghua Univ., Beijing (China)
  2. Chinese Academy of Sciences (CAS), Shanghai (China)
  3. Brown Univ., Providence, RI (United States)
  4. Tsinghua Univ., Beijing (China); Chinese Academy of Sciences (CAS), Shanghai (China)
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
+ Show Author Affiliations

We report a joint photoelectron spectroscopy and theoretical investigation of the gaseous Au2I3– cluster, which is found to exhibit two types of isomers due to competition between Au–I covalent bonding and Au–Au aurophilic interactions. The covalent bonding favors a bent IAuIAuI– structure with an obtuse Au–I–Au angle (100.7°), while aurophilic interactions pull the two Au atoms much closer, leading to an acutely bent structure (72.0°) with an Au–Au distance of 3.08 Å. The two isomers are separated by a small barrier and are nearly degenerate with the obtuse isomer being slightly more stable. At low temperature, only the obtuse isomer is observed; distinct experimental evidence is observed for the co-existence of a combination of isomers with both acute and obtuse bending angles at room temperature. As a result, the two bond-bending isomers of Au2I3– reveal a unique example of one molecule being able to oscillate between different structures as a result of two competing chemical forces.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
1263745; 21433005, 21201106, and 21221062; AC52-06NA25396
OSTI ID:
1239322
Report Number(s):
LA-UR-15-21694; CSHCBM
Journal Information:
Chemical Science, Vol. 7, Issue 1; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

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Making the unconventional μ 2 -P bridging binding mode more conventional in phosphinine complexes journal January 2019
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ab initio calculation
bond-bending isomer
aurophilicity
photoelectron spectroscopy
chemical bonding