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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >HC P and H3C-C P as proton acceptors in protonated complexes containing two phosphorus bases: Structures, binding energies, and spin-spin coupling constants
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HC P and H3C-C P as proton acceptors in protonated complexes containing two phosphorus bases: Structures, binding energies, and spin-spin coupling constants

机译：HC P和H3C-C P作为质子受体的质子受体，含两个磷碱基：结构，结合能和自旋-自旋偶合常数

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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, sp(2), and sp(3) phosphorus bases as proton donor ions and the sp-hybridized phosphorus bases H-C P and H3C-C P as proton acceptors. These proton-bound complexes exhibit a variety of structural motifs, but all are stabilized by interactions that occur through the T cloud of the acceptor base. The binding energies of these complexes range from 6 to 15 kcal/mol. Corresponding complexes with H3C-C P as the proton acceptor are more stable than those with H-C P as the acceptor, a reflection of the greater basicity of H3C-C P. In most complexes with sp(2)- or sp(3)-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 P bond and a red shift of he C 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 (2hJ)(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，sp（2）和sp（3）磷碱基作为质子供体离子的阳离子配合物的结构和结合能。 sp杂化的磷碱基HC P和H3C-C P作为质子受体。这些与质子结合的复合物表现出多种结构基序，但是所有这些都通过通过受体碱基的T云发生的相互作用而稳定。这些配合物的结合能为6至15kcal / mol。以H3C-C P为质子受体的相应配合物比以HC P为质子受体的配合物更稳定，这反映了H3C-C P的更强碱性。在大多数以sp（2）-或sp（3）-杂化的PH供体离子，PH键加长，PH拉伸频率相对于相应的单体发生红移。络合物的形成还导致CP键的延长和CP拉伸振动的红移。对于其中发生氢键结合的配合物，两键耦合常数（2 pi h）J（PP）和（2 pi h）J（PC）显着小于（2h）J（pP）和（2hJ）（PC）通过P或C上的孤对电子。这反映出在这些pi配合物的氢键区域中没有显着的s电子密度。

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