Detection of Free Monomeric Silver(I) and Gold(I) Cyanides, AgCN and AuCN: Microwave Spectra and Molecular Structure

Abstract

The chemistry of the group 11 metal cyanide system has been of considerable interest because of the commercial importance of some of the complexes formed in this system. These metal cyanides contain one-dimensional linear -M-CN-M-CN-M- chains in the solid state; however, they have not been observed as free monomeric species. This Article reports the first detection of monomeric AgCN and AuCN in the gas phase by using rotational spectroscopy. The sputtering reaction of silver and/or gold sheets placed on a stainless steel cathode with CH3CN diluted in Ar resulted in the production of AgCN and AuCN spectra. Spectroscopic observation of the parent and several rare isotopic species allowed the determination of r(0), r(s), r(Iepsilon), r(m)(1), and r(m)(2) structures in the case of AgCN and r(0) and r(s) structures in the case of AuCN. All data indicate that these two species have a linear MCN geometry with a low-energy bending vibration.

Ab initio ro-vibrational spectroscopy of the group 11 cyanides: CuCN, AgCN, and AuCN

“…The experimental values of B 0 are also given in Table IV for CuCN, 6 AgCN 7 and AuCN. 7 The theoretical results in Table IV Table IV. Of course the resulting anharmonic frequencies computed with these anharmonicities are also significantly affected.…”

“…Experimental data on the monomeric gas-phase group 11 cyanides have been produced using microwave spectroscopy, 6,7 photoelectron spectroscopy, 8 and photoelectron velocity-map imaging 3 as mentioned above. These experiments have yielded accurate rotational constants, estimates of some of the vibrational frequencies, and their electron affinities.…”

“…In the case of AgCN, the rotational constant in ν 3 =1 was obtained from the microwave spectroscopy experiments of Okabayashi et al, 7 and as shown in Table VI it is smaller than the ground state value as is typically the case for a stretching fundamental. This yields a B 0 -B v value that is in good agreement with the value of α 3 obtained from vibrational perturbation theory (Table IV) In order to further examine the accuracy of the equilibrium structures produced by the composite method, semi-experimental equilibrium geometries (r e SE ) were calculated by combining the ab initio rotation-vibration interaction constants (α i ) of Table IV with experimental values 59 of the ground state rotational constants B 0 via the Kraitchman equations.…”

Solvent Acting as a Precursor: Synthesis ofAgCNFromAgNO3inN,N‐DMFSolvent by Laser Ablation

“…Metal cyanides are of considerable interest owing to their commercial importance. For example, AuCN and AgCN are used in mining, electroplating, and photography . However, many typical methods for the synthesis of metal cyanides mostly use cyanide ions, toxic anions, and it can induce many health problems, especially in the vascular, visual, central nervous, cardiac, endocrine, and metabolic systems .…”

“…For example, AuCN and AgCN are used in mining, electroplating, and photography. 1,2 However, many typical methods for the synthesis of metal cyanides mostly use cyanide ions, toxic anions, and it can induce many health problems, especially in the vascular, visual, central nervous, cardiac, endocrine, and metabolic systems. 3,4 It is known that 0.5-3.5 mg of cyanide/kg of body weight is fatal for humans.…”