Cho Han-Gook, Andrews Lester S
Department of Chemistry, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon 22012, South Korea.
Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319, United States.
Inorg Chem. 2021 May 3;60(9):6421-6432. doi: 10.1021/acs.inorgchem.1c00132. Epub 2021 Apr 15.
Reactions of group 11 metals with cyanogen, N≡C-C≡N, in excess argon and neon have been carried out, and the products were identified via examination of the matrix spectra and their variation upon photolysis, annealing, and isotopic substitutions. Density functional theory calculations provided helpful information for the plausible products and reaction paths. While M···NCCN and M···CNCN were observed in all three metal systems, the cyanide and isocyanide products (NCMCN, NCMNC, and CNMNC) were identified only in the Cu reactions, and M···C(N)CN was identified in the Cu and Au spectra. Intrinsic reaction coordinate calculation results along with the observed spectral variation upon photolysis and annealing suggest that Cu···C(N)CN was the pathway to cyanide and isocyanide. The product absorptions with exceptionally high C-N stretching frequencies in the Au system have been tentatively assigned to a cation [Au···NCCN]. The group 11 metal cyanides and isocyanides that require two chemical bonds to the central metal are energetically favorable only in the lightest metal system.
在过量氩气和氖气中，对第11族金属与氰（N≡C-C≡N）的反应进行了研究，并通过检查基质光谱及其在光解、退火和同位素取代后的变化来鉴定产物。密度泛函理论计算为可能的产物和反应路径提供了有用信息。虽然在所有三种金属体系中都观察到了M···NCCN和M···CNCN，但仅在铜的反应中鉴定出了氰化物和异氰化物产物（NCMCN、NCMNC和CNMNC），并且在铜和金的光谱中鉴定出了M···C(N)CN。本征反应坐标计算结果以及光解和退火后观察到的光谱变化表明，Cu···C(N)CN是生成氰化物和异氰化物的途径。在金体系中具有异常高的C-N伸缩频率的产物吸收被初步归属于阳离子[Au···NCCN]。需要与中心金属形成两个化学键的第11族金属氰化物和异氰化物仅在最轻的金属体系中在能量上是有利的。
