Issue 7, 2019

The HKrCCH⋯CO2 complex: an ab initio and matrix-isolation study

Abstract

We report an experimental and theoretical study on new noble-gas hydride complex HKrCCH⋯CO2, which is the first known complex of a krypton hydride with carbon dioxide. This species was prepared by the annealing-induced H + Kr + CCH⋯CO2 reaction in a krypton matrix, the CCH⋯CO2 complexes being produced by UV photolysis of propiolic acid (HCCCOOH). The H–Kr stretching mode of the HKrCCH⋯CO2 complex at 1316 cm−1 is blue-shifted by 74 cm−1 from the most intense H–Kr stretching band of HKrCCH monomer. The observed blue shift indicates the stabilization of the H–Kr bond upon complexation, which is characteristic of complexes of noble-gas hydrides. This spectral shift is slightly larger than that of the HKrCCH⋯C2H2 complex (+60 cm−1) and significantly larger than that of the HXeCCH⋯CO2 complex (+32 and +6 cm−1). On the basis of comparison with ab initio computations at the MP2 and CCSD(T) levels of theory, the experimentally observed absorption is assigned to the quasi-parallel configuration of the HKrCCH⋯CO2 complex. The calculated complexation-induced spectral shift of the H–Kr stretching band (60.4 or 72.7 cm−1 from the harmonic calculations at the MP2 and CCSD(T) levels, respectively) agrees well with the experimental value.

Graphical abstract: The HKrCCH⋯CO2 complex: an ab initio and matrix-isolation study

Supplementary files

Article information

Article type
Paper
Submitted
09 7月 2018
Accepted
01 11月 2018
First published
05 11月 2018

Phys. Chem. Chem. Phys., 2019,21, 3656-3661

The HKrCCH⋯CO2 complex: an ab initio and matrix-isolation study

S. V. Ryazantsev, D. A. Tyurin, K. B. Nuzhdin, V. I. Feldman and L. Khriachtchev, Phys. Chem. Chem. Phys., 2019, 21, 3656 DOI: 10.1039/C8CP04327B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements