• 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 >HC ident to P and H3C-C ident to P as Proton Acceptors in Protonated Complexes Containing Two Phosphorus Bases:Structures,Binding Energies,and Spin-Spin Coupling Constants
【24h】

HC ident to P and H3C-C ident to P as Proton Acceptors in Protonated Complexes Containing Two Phosphorus Bases:Structures,Binding Energies,and Spin-Spin Coupling Constants

机译：HC与P结合，H3C-C与P结合，作为质子受体，质子含两个磷碱基：结构，结合能和自旋-自旋耦合常数

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

Ab initio calculations at the MP2/aug'-cc-pVTZ level have been carried out to investigate the structures and binding energies of cationic complexes involving protonated sp,sp2,and sp3 phosphorus bases as proton donor ions and the sp-hybridized phosphorus bases H-C ident to P and H3C-C ident to P as proton acceptors.These proton-bound complexes exhibit a variety of structural motifs,but all are stabilized by interactions that occur through the pi cloud of the acceptor base.The binding energies of these complexes range from 6 to 15 kcal/mol.Corresponding complexes with H3C-C ident to P as the proton acceptor are more stable than those with H-C ident to P as the acceptor,a reflection of the greater basicity of H3C-C ident to P.In most complexes with sp2-or sp3-hybridized P-H donor ions,the P-H bond lengthens and the P-H stretching frequency is red-shifted relative to the corresponding monomers.Complex formation also leads to a lengthening of the C ident to P bond and a red shift of the C ident to P stretching vibration.The two-bond coupling constants ~(2 pi h)J(P-P)and ~(2 pi h)J(P-C)are significantly smaller than ~(2h)J(P-P)and ~(2h)J(P-C)for complexes in which hydrogen bonding occurs through lone pairs of electrons on P or C.This reflects the absence of significant s electron density in the hydrogen-bonding regions of these pi complexes.
机译：已进行了MP2 / aug'-cc-pVTZ水平的从头算计算，以研究涉及质子化的sp，sp2和sp3磷碱作为质子供体离子和sp杂化的磷碱HC的阳离子配合物的结构和结合能。这些与质子结合的配合物表现出多种结构基序，但通过受主基团的pi云发生相互作用而稳定化。这些配合物的结合能范围很广。从6到15 kcal / mol.H3C-C等同于P作为质子受体的相应配合物比HC HC等同于P作为质子受体的配合物更稳定，反映出H3C-C ident对P.In具有更大的碱性大多数带有sp2-或sp3-杂化的PH供体离子的配合物，PH键加长且PH拉伸频率相对于相应的单体发生红移。复合物的形成还导致C ident延长为P键并发生红移C的与（2 pi h）J（PP）和〜（2 pi h）J（PC）的双键耦合常数明显小于〜（2h）J（PP）和〜（2h） J（PC）用于其中氢通过P或C上的孤对电子发生键合的配合物，这反映出在这些pi配合物的氢键区域中不存在显着的s电子密度。

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