Detailed Information on Publication Record

LANTTO, Perttu, Stanislav STANDARA, Sebastian RIEDEL, Juha VAARA and Michal STRAKA. Exploring new 129Xe chemical shift ranges in HXeY compounds: hydrogen more relativistic than xenon. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2012, vol. 14, No 31, p. 10944-10952. ISSN 1463-9076. Available from: https://dx.doi.org/10.1039/C2CP41240C.

Other formats: BibTeX LaTeX RIS

Basic information
Original name	Exploring new 129Xe chemical shift ranges in HXeY compounds: hydrogen more relativistic than xenon
Authors	LANTTO, Perttu (246 Finland), Stanislav STANDARA (203 Czech Republic, guarantor, belonging to the institution), Sebastian RIEDEL (276 Germany), Juha VAARA (246 Finland) and Michal STRAKA (203 Czech Republic).
Edition	Physical Chemistry Chemical Physics, Cambridge, Royal Society of Chemistry, 2012, 1463-9076.

Other information
Original language	English
Type of outcome	Article in a journal
Field of Study	10403 Physical chemistry
Country of publisher	United Kingdom of Great Britain and Northern Ireland
Confidentiality degree	is not subject to a state or trade secret
WWW	URL
Impact factor	Impact factor: 3.829
RIV identification code	RIV/00216224:14740/12:00074606
Organization unit	Central European Institute of Technology
Doi	http://dx.doi.org/10.1039/C2CP41240C
UT WoS	000306572600014
Keywords in English	COUPLED-CLUSTER CALCULATIONS; DENSITY-FUNCTIONAL CALCULATIONS; RESONANCE SHIELDING TENSORS; NOBLE-GAS ATOMS; RARE-GAS; AB-INITIO; SPECTROSCOPIC PARAMETERS; NUCLEAR SHIELDINGS; MATRIX-ISOLATION; NMR PROPERTIES
Tags	129Xe NMR, BPPT, chemical shifts, kontrola MP, NMR, Quantum Chemical Calculations, relativistic effects, rivok, Xenon
Tags	International impact, Reviewed
Changed by	Changed by: Olga Křížová, učo 56639. Changed: 9/6/2014 09:24.

Abstract
Among rare gases, xenon features an unusually broad nuclear magnetic resonance (NMR) chemical shift range in its compounds and as a non-bonded Xe atom introduced into different environments. In this work we show that 129Xe NMR chemical shifts in the recently prepared, matrix-isolated xenon compounds appear in new, so far unexplored 129Xe chemical shift ranges. State-of-the-art theoretical predictions of NMR chemical shifts in compounds of general formula HXeY (Y = H, F, Cl, Br, I, -CN, -NC, -CCH, -CCCCH, -CCCN, -CCXeH, -OXeH, -OH, -SH) as well as in the recently prepared ClXeCN and ClXeNC species are reported. The bonding situation of Xe in the studied compounds is rather different from the previously characterized cases as Xe appears in the electronic state corresponding to a situation with a low formal oxidation state, between I and II in these compounds. Accordingly, the predicted 129Xe chemical shifts occur in new NMR ranges for this nucleus: ca. 500-1000 ppm (wrt Xe gas) for HXeY species and ca. 1100-1600 ppm for ClXeCN and ClXeNC. These new ranges fall between those corresponding to the weakly-bonded Xe0 atom in guest–host systems (>300 ppm) and in the hitherto characterized Xe molecules (<2000 ppm). The importance of relativistic effects is discussed. Relativistic effects only slightly modulate the 129Xe chemical shift that is obtained already at the nonrelativistic CCSD(T) level. In contrast, spin–orbit-induced shielding effects on the 1H chemical shifts of the H1 atom directly bonded to the Xe center largely overwhelm the nonrelativistic deshielding effects. This leads to an overall negative 1H chemical shift in the range between -5 and -25 ppm (wrt CH4). Thus, the relativistic effects induced by the heavy Xe atom appear considerably more important for the chemical shift of the neighbouring, light hydrogen atom than that of the Xe nucleus itself. The predicted NMR parameters facilitate an unambiguous experimental identification of these novel compounds.

Abstract

Among rare gases, xenon features an unusually broad nuclear magnetic resonance (NMR) chemical shift range in its compounds and as a non-bonded Xe atom introduced into different environments. In this work we show that 129Xe NMR chemical shifts in the recently prepared, matrix-isolated xenon compounds appear in new, so far unexplored 129Xe chemical shift ranges. State-of-the-art theoretical predictions of NMR chemical shifts in compounds of general formula HXeY (Y = H, F, Cl, Br, I, -CN, -NC, -CCH, -CCCCH, -CCCN, -CCXeH, -OXeH, -OH, -SH) as well as in the recently prepared ClXeCN and ClXeNC species are reported. The bonding situation of Xe in the studied compounds is rather different from the previously characterized cases as Xe appears in the electronic state corresponding to a situation with a low formal oxidation state, between I and II in these compounds. Accordingly, the predicted 129Xe chemical shifts occur in new NMR ranges for this nucleus: ca. 500-1000 ppm (wrt Xe gas) for HXeY species and ca. 1100-1600 ppm for ClXeCN and ClXeNC. These new ranges fall between those corresponding to the weakly-bonded Xe0 atom in guest–host systems (>300 ppm) and in the hitherto characterized Xe molecules (<2000 ppm). The importance of relativistic effects is discussed. Relativistic effects only slightly modulate the 129Xe chemical shift that is obtained already at the nonrelativistic CCSD(T) level. In contrast, spin–orbit-induced shielding effects on the 1H chemical shifts of the H1 atom directly bonded to the Xe center largely overwhelm the nonrelativistic deshielding effects. This leads to an overall negative 1H chemical shift in the range between -5 and -25 ppm (wrt CH4). Thus, the relativistic effects induced by the heavy Xe atom appear considerably more important for the chemical shift of the neighbouring, light hydrogen atom than that of the Xe nucleus itself. The predicted NMR parameters facilitate an unambiguous experimental identification of these novel compounds.

Links
ED1.1.00/02.0068, research and development project	Name: CEITEC - central european institute of technology