Can Copper(I) and Silver(I) be Hydrogen Bond Acceptors?
Erik Andris, Michal Straka, Jan Vrána, Aleš Růžička, Jana Roithová, Lubomı́r Rulı́šek
Abstract
Abstract Gold(I) centers can form moderately strong (Au⋅⋅⋅H) hydrogen bonds with tertiary ammonium groups, as has been demonstrated in the 3AuCl + ( 3 + =1‐( tert ‐butyl)‐3‐phenyl‐4‐(2‐((dimethylammonio)methyl)phenyl)‐1,2,4‐triazol‐5‐ylidene) complex. However, similar hydrogen bonding interactions with isoelectronic silver(I) or copper(I) centers are unknown. Herein, we first explored whether the Au⋅⋅⋅H bond originally observed in 3AuCl + can be strengthened by replacing Cl with Br or I. Experimental gas‐phase IR spectra in the ∼3000 cm −1 region showed only a small effect of the halogen on the Au⋅⋅⋅H bond. Next, we measured the spectra of 3AgCl + , which exhibited significant differences compared to its 3AuX + counterparts. The difference has been explained by DFT calculations which indicated that the Ag⋅⋅⋅H interaction is only marginal in this complex, and a Cl⋅⋅⋅H hydrogen bond is formed instead. Calculations predicted the same for the 3CuCl + complex. However, we noticed that for Ag and Cu complexes with less flexible ligands, such as dimethyl(2‐(dimethylammonio)phenyl)phosphine (L 7 H + ), the computations predict the presence of the respective Ag⋅⋅⋅H and Cu⋅⋅⋅H hydrogen bonds, with a strength similar to the Au⋅⋅⋅H bond in 3AuCl + . We, therefore, propose possible complexes where the presence of (Ag/Cu)⋅⋅⋅H bonds could be experimentally verified to broaden our understanding of these unusual interactions.