Hydrogen-Atom Tunneling in Metaphosphorous Acid
Weiyu Qian+,[a] Xianxu Chu+,[a] Chao Song[a], Zhuang Wu[a], Mengqi Jiao[a], Hanwen Liu[a],Bin Zou[a], Guntram Rauhut[b], David P. Tew[c], Lina Wang[d], and Xiaoqing Zeng*[a, d](曾小庆)
[a] College of Chemistry Chemical Engineering and Materials Science
Soochow University,215123 Suzhou (China)
[b] Institute for Theoretical Chemistry,University of Stuttgart Pfaffenwaldring 55, Stuttgart 70569 (Germany)
[c] Max-Planck Institute for Solid State Research Heisenbergstraße 1, Stuttgart 70569 (Germany)
[d] Department of Chemistry,Fudan University,Shanghai 200433 (China)
[+] These authors contributed equally to this work.
Chem. Eur. J.2020, 26, 8205--8209
Metaphosphorous acid (HOPO), a key intermediate in phosphorus chemistry, has been generated in syn‐ and anti‐conformations in the gas phase by high‐vacuum flash pyrolysis (HVFP) of a molecular precursor ethoxyphosphinidene oxide (EtOPO→C2H4+HOPO) at ca. 1000 K and subsequently trapped in an N2‐matrix at 2.8 K. Unlike the two conformers of the nitrogen analogue HONO, the anti‐conformer of HOPO undergoes spontaneous rotamerization at 2.8 K via hydrogen‐atom tunneling (HAT) with noticeable kinetic isotope effects for H/D (>104 for DOPO) and 16O/18O (1.19 for H18OPO and 1.06 for HOP18O) in N2‐matrices.
链接:https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202000844