基质隔离分子复合物CO/XF（X = Cl、Br、I）及FC(O)Br的分子结构

The matrix-isolated molecular complexes CO/XF (X=Cl,Br,I) and the molecular structure of FC(O)Br.

作者信息

García Plácido, Willner Helge, Oberhammer Heinz, Francisco Joseph S

机构信息

FB C, Anorganische Chemie, Bergische Universität Wuppertal, Gaussstrasse 20, D-42097 Wuppertal, Germany.

出版信息

J Chem Phys. 2004 Dec 15;121(23):11900-6. doi: 10.1063/1.1814634.

DOI:10.1063/1.1814634

PMID:15634151

Abstract

FC(O)Br has been synthesized, and its IR spectrum in the gas phase and isolated in an Ar matrix, as well as, its Raman spectrum in the solid state at -196 degrees C has been analyzed. Its molecular structure has been determined and its UV has been measured. FC(O)Br and FC(O)Cl has been photodissociated in an argon matrix at 17 K with a 193 nm laser. The photolysis produces CO and XF which recombine to form CO/XF complexes. The formation of complexes are followed by the shift of the normal vibration modes with respect to CO and XF isolated in argon matrix. In the case of FC(O)Br, three isomers are identified, OC...BrF, OC...FBr, and CO...BrF, whereas for FC(O)Cl only one isomer is observed, OC...ClF. High level quantum chemical calculations are used to help the assignment of the different isomers.

摘要

已合成了FC(O)Br，并分析了其在气相中以及在氩基质中分离时的红外光谱，还有其在-196℃固态下的拉曼光谱。已确定其分子结构并测量了其紫外光谱。FC(O)Br和FC(O)Cl在17K的氩基质中用193nm激光进行了光解离。光解产生CO和XF，它们重新结合形成CO/XF络合物。通过相对于在氩基质中分离的CO和XF的正常振动模式的位移来跟踪络合物的形成。对于FC(O)Br，鉴定出三种异构体，OC...BrF、OC...FBr和CO...BrF，而对于FC(O)Cl，仅观察到一种异构体，OC...ClF。使用高水平量子化学计算来辅助不同异构体的归属。