...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Infrared spectra of CX_2=CoX_2 and CX_3-CoX complexes from reactions of laser-ablated cobalt atoms with halomethanes
【24h】

Infrared spectra of CX_2=CoX_2 and CX_3-CoX complexes from reactions of laser-ablated cobalt atoms with halomethanes

机译：激光烧蚀钴原子与卤代甲烷反应生成的CX_2 = CoX_2和CX_3-CoX配合物的红外光谱

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Simple cobalt complexes with substantial carbon-cobalt double bond character are produced in Co atom reactions with tetra-, tri-, and dihalomethanes, whereas insertion complexes are identified only in the dihalomethane matrix infrared spectra. These complexes are identified from matrix infrared spectra and comparison with frequencies computed by density functional theory. Exclusive generation of carbenes in the tetrahalomethane systems is consistent with the computational results that the staggered allene-type conformer is the only meaningful energy minimum in the reaction path. Their short C-Co bondlengths of 1.732-1.764 ? and CASSCF computed bond orders near 1.7 are also appropriate for carbon-cobalt double bonds. Hence, reactions of laser-ablated Co atoms are effective means to generate rarely reported high oxidation-state Co complexes with carbon-cobalt double bonds. Unlike the Rh and Ir cases, Co carbynes (with C-Co triple bonds) are not formed. The observation of CH_2Cl-CoF with photoreversible intensity variation in the spectra provides unique insight on halogen migration from interconversion with CH_2F-CoCl through the CH_2=CoFCl carbene.
机译：具有四碳，三碳和二卤甲烷的Co原子反应生成具有大量碳-钴双键特征的简单钴络合物，而插入络合物仅在二卤甲烷基质红外光谱中鉴定。从基质红外光谱中识别这些配合物，并与密度泛函理论计算的频率进行比较。在四卤甲烷系统中仅生成碳烯与计算结果一致，即交错的异戊二烯型构象异构体是反应路径中唯一有意义的最小能量。它们的短C-Co键长为1.732-1.764？和CASSCF计算的1.7左右的债券定单也适用于碳-钴双键。因此，激光烧蚀的Co原子的反应是产生很少报道的具有碳-钴双键的高氧化态Co络合物的有效手段。与Rh和Ir情况不同，不会形成Co卡宾（具有C-Co三键）。光谱中具有光可逆强度变化的CH_2Cl-CoF的观察结果提供了关于卤素从CH_2F-CoCl相互转化通过CH_2 = CoFCl卡宾的迁移的独特见解。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号