Cho Han-Gook, Andrews Lester
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. 2020 Oct 19;59(20):15438-15446. doi: 10.1021/acs.inorgchem.0c02436. Epub 2020 Oct 8.
Reactions of laser-ablated silver atoms with tetrahalomethanes have been carried out in excess argon, and the products were identified via examination of the matrix spectra and their variation on photolysis and annealing. While production of the insertion products (CX-AgX) was evident in all Ag reactions, different sets of product absorptions were also observed in the higher frequency region (1260-720 cm). They increased on photolysis but decreased on annealing, opposite to the absorptions of the insertion products. They have been assigned to weakly bound complexes of CX and AgX (XCX···AgX), which were generated in halogen abstraction by the metal atom from CX. These Cl-mediated Ag complexes are only slightly higher in energy than the insertion products due to the ds electron configuration of the group 11 metal. NBO analyses reveal that the CX radical is coordinated to an ionic species (AgCl) via electron-rich X. The product absorptions marked "" in the previous Au + CX study also most probably originated from the weakly bound product, which is more stable than the methylidene (XC-AuX).
在过量氩气中进行了激光烧蚀银原子与四卤代甲烷的反应，并通过检查基质光谱及其在光解和退火时的变化来鉴定产物。虽然在所有银反应中插入产物（CX-AgX）的生成是明显的，但在较高频率区域（1260 - 720 cm）也观察到了不同组的产物吸收。它们在光解时增加，但在退火时减少，这与插入产物的吸收情况相反。它们被归属于CX和AgX的弱结合络合物（XCX···AgX），这是金属原子从CX中进行卤素提取时生成的。由于第11族金属的ds电子构型，这些由氯介导的银络合物的能量仅比插入产物略高。自然键轨道分析表明，CX自由基通过富电子的X与离子物种（AgCl）配位。在之前金与CX的研究中标记为“”的产物吸收很可能也源自弱结合产物，该产物比亚甲基（XC-AuX）更稳定。
