Gold(I) Hydrides as Proton Acceptors in Dihydrogen Bond Formation

作者：Cukrowski Ignacy^*; de lange Jurgens H; Groenewald Ferdinand; Raubenheimer Helgard G^*

来源：ChemPhysChem, 2017, 18(16): 2288-2294.

DOI：10.1002/cphc.201700383

• dihydrogen bonds
• Eigen complex analogues
• gold hydrides
• quantum chemical calculations
• sigma-dihydrogen gold complexes

Wavefunction and DFT calculations indicate that anionic dihydride complexes of Au-I form strong to moderate directed Au-H center dot center dot center dot H bonds with one or two HF, H2O and NH3 prototype proton donor molecules. The largely electrostatic interaction is influenced by relativistic effects which, however, do not increase the binding energy. Very weak Au center dot center dot center dot H associations-exhibiting a corresponding bond path-occur between neutral AuH and HF units, although ultimately F becomes the preferred donor atom in the most stable structure. Increasing the hydridicity of AuH by attachment of an electron donating NHC ligand effects Au-H center dot center dot center dot H bonding of moderate strength only with HF, whereas competing Au center dot center dot center dot H interactions dominate for H2O and NH3. Rare eta(2) coordinated and HX (X=F or OH) associated H-2 complexes are produced during interaction with a single ion of stronger acidity, H2F+ or H3O+. Theoretically, reaction of excess [AuH2](-) as proton acceptor with H3O+ or NH4+ in 3: 1 or 4: 1 ionic ratios, respectively, affords H center dot center dot center dot H bonded analogues of Eigen-type adducts. Outstanding analytical relationships between selected bonding parameters support the integrity of the results.

• 出版日期2017-8-18