The Synthesis of [2-2H1]Thiirane-1-oxide and [2,2-2H2]Thiirane-1-oxide and the Diastereoselective Infrared Laser Chemistry of [2-2H1]Thiirane-1-oxide

Gross, Heike; Grassi, G.; Qüack, Martin

doi:10.1002/(sici)1521-3765(19980310)4:3<441::aid-chem441>3.0.co;2-3

Cited by 17 publications

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References 25 publications

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“…High-resolution analyses of the IR spectra of chiral molecules are still very scarce. They provide a necessary first step toward further experiments designed for detecting molecular parity violation as discussed in Quack (1986Quack ( , 1989bQuack ( , 2002, Daussy et al (1999), Laerdahl et al (2000), Hollenstein et al (1997), Quack and Stohner (2000, 2003, Gross et al (1998), Quack and Willeke (2006), Berger and Quack (2000a,b). This kind of effort provides a connection between molecular spectroscopy and fundamental high-energy physics.…”

Section: Discussionmentioning

confidence: 95%

“…Very few rovibrational spectral analyses of chiral or isotopically chiral molecules have been reported to date, for CHBrClF (Bauder et al 1997), fluorooxirane c-C 2 FH 3 O , substituted thiiran-1-oxides (Gross et al 1998), CDBrClF (Albert and Quack 2001, Albert et al 2001a, 2003b, CH 35 Cl 37 ClF (Snels and Quack 1991, Albert et al 2004a, Albert and Quack 2007b and C 2 H 3 DO (Albert et al 2003a), CHClFI (Soulard et al 2006) (in an approach following closely the original work on CHBrClF (Bauder et al 1997, Beil et al 1994a) and very recently CHBrIF (Albert et al 2008b,c), aziridine-2-carbonitrile (C 3 H 4 N 2 ), (Albert et al 2008a), and oxirane carbonitrile (C 3 H 3 NO), (Albert et al 2009a), see also Quack 2011: Fundamental Symmetries and Symmetry Violations from High-resolution Spectroscopy, this handbook.…”

Section: Overview Of the Articlementioning

confidence: 99%

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High‐Resolution Fourier Transform Infrared Spectroscopy

Albert

Qüack

2011

Handbook of High‐resolution Spectroscopy

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Recent developments and applications of high‐resolution Fourier transform spectroscopy are reviewed. A short historical summary of the development of high‐resolution interferometric Fourier transform infrared (FTIR) spectrometers is given and the possibilities of the currently most highly resolving FTIR spectrometers, including a current prototype built for the Zürich group at the Swiss Light Source SLS as a synchrotron light source, are discussed. A short description of the principles of FTIR spectroscopy is given and the resolution of current spectrometers is illustrated by FTIR spectra of CO, CO 2 OCS, N 2 O, CS 2 , and CH 4 and its isotopomers. The computational tools necessary to analyze FTIR spectra are described briefly. As examples of rovibrational analysis of more complex spectra, selected molecules CHCl 2 F, CDBrClF, pyridine (C 6 H 5 N) and pyrimidine (C 4 H 4 N 2 ), and naphthalene (C 10 H 8 ) are discussed. The spectrum of CHCl 2 F, a fluorochlorocarbon, is of interest for a better understanding of the chemistry of the Earth's atmosphere. It also possesses an isotopically chiral isotopomer CH 35 Cl 37 ClF analyzed in natural abundance. CDBrClF is a chiral molecule and therefore the analysis of its rovibrational spectra provides the basis for carrying out further experiments toward the detection of molecular parity violation. The analyses of the pyridine, pyrimidine, and naphthalene FTIR spectra illustrate the potential of the new generation of FTIR spectrometers in the study of spectra and rovibrational dynamics of aromatic systems and molecules of potential biological interest. In particular, naphthalene is a prototype molecule useful in gaining an understanding of the unidentified infrared bands (UIBs) detected in several interstellar objects.

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Section: Discussionmentioning

confidence: 95%

Section: Overview Of the Articlementioning

confidence: 99%

High‐Resolution Fourier Transform Infrared Spectroscopy

Albert

Qüack

2011

Handbook of High‐resolution Spectroscopy

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“…Eine Voraussetzung für jedes derartige Experiment zum Nachweis der Paritätsverletzung ebenso wie für die vorgeschlagene direkte Messung von Δ pv E 4 ist das aufgelöste und analysierte Schwingungsrotationsspektrum des zu untersuchenden chiralen Moleküls. Nach unserer Kenntnis gab es bis 1994 kein einziges Beispiel, wo eine solche Analyse für ein chirales Molekül gelungen wäre, seitdem konnten wir aber drei Verbindungen erfolgreich IR‐spektroskopisch analysieren: CHBrClF,6, 23 2‐Fluoroxiran24 und (2,2‐ 2 H 2 )Thiiran‐1‐oxid 25, 26…”

Section: Die Wichtigsten Parameter P̃0 P̃1 P̃2 [10−15 Cm−1] Die Duunclassified

Paritätsverletzung in Fluoroxiran

2001

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Professor Paul von RagueÂ Schleyer zum 70. Geburtstag gewidmetVor mehr als einem Jahrhundert hat van t Hoff [1] bereits darauf hingewiesen, dass die Bildungswärme und die Entropie von Enantiomeren chiraler Verbindungen aus Symmetriegründen genau gleich sein müssen. Die traditionelle Quantenchemie, die nur die elektromagnetische Wechselwirkung berücksichtigt, findet tatsächlich diese Symmetrie. [2] Dagegen sagt die elektroschwache Quantenchemie einen Energie-und Entropieunterschied infolge der Paritätsverletzung voraus. Eine der gröûten Herausforderungen unseres gegenwärtigen Verständnisses grundlegender Aspekte der Struktur und Dynamik chiraler Moleküle ist der experimentelle Beweis dieser Konsequenzen der Paritätsverletzung. [3] Schon seit geraumer Zeit werden hierzu spektroskopische Eperimente vorgeschlagen. Einige dieser Ansätze zielen auf die direkte Messung der Reaktionsenthalpie D r H 0 0 für die Umwandlung von (S)-in (R)-Enantiomere, die mit dem Energieunterschied infolge der Paritätsverletzung (pv), D pv E, [3,4] nach Gleichung (1) verknüpft ist.Andere Ansätze beruhen auf der Messung von Frequenzverschiebungen in den NMR-, [5] Mikrowellen-, [6] IR- [6±10] oder Möûbauer-Spektren [11] von (R)-und (S)-Enantiomeren (siehe Diagramm in Abbildung 1).Die theoretische Vorhersage, [12,13] dass die durch die Paritätsverletzung in chiralen Molekülen hervorgerufenen Effekte typischerweise um ein bis zwei Gröûenordnungen gröûer sind als bisher angenommen, [14,15] hat ein verstärktes theoretisches [16±22] und experimentelles Interesse [6,10,11] an diesem Forschungsgebiet geweckt.Besonders wichtig sind hierbei Experimente an chiralen Molekülen im niederfrequenten ¹optischenª (infraroten [10] ) Spektralbereich, wo die momentan beste relative Frequenzgenauigkeit von etwa 10 À13 im Bereich der CO 2 -Laseremission um 1000 cm À1 erreicht wurde. Die relative Unsicherheit in der Frequenz ist aber immer noch drei bis vier Zehnerpotenzen gröûer, als etwa Rechnungen für Frequenzverschiebungen am Abbildung 1. Die Energiezustände und die Strukturen der Fluoroxiran-Enantiomere. Die Struktur von (R)-Fluoroxiran (rechts), die in allen Rechnungen verwendet wurde, wurde aus einer vollständigen MP2-Geometrieoptimierung mit einer TZ2P-Basis erhalten; sie ist in Übereinstimmung mit experimentellen Daten aus hochauflösender Spektroskopie. [24] Die gestrichelte Linie deutet an, dass eine direkte optische Anregung zu diesem (S)-Zustand ausgehend vom (R)-Grundzustand verboten ist.Prototypmolekül CHBrClF vorhersagen. [20±22] Eine Voraussetzung für jedes derartige Experiment zum Nachweis der Paritätsverletzung ebenso wie für die vorgeschlagene direkte Messung von D pv E [4] ist das aufgelöste und analysierte Schwingungsrotationsspektrum des zu untersuchenden chiralen Moleküls. Nach unserer Kenntnis gab es bis 1994 kein einziges Beispiel, wo eine solche Analyse für ein chirales Molekül gelungen wäre, seitdem konnten wir aber drei Verbindungen erfolgreich IR-spektroskopisch analysieren: CHBrClF, [6,23] 2-Fluoroxiran [24] und (2,2-2 H 2 )Thiiran-...

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“…A prerequisite for any such experiment, as well as for the proposed direct measurement of Δ pv E 4 is a rovibrationally line resolved and analyzed optical spectrum of the chiral molecule under consideration. While until 1994 there was to our knowledge not a single example where such an analysis had been achieved for a chiral molecule, since that time three cases in parallel have been successfully studied in our laboratory: CHBrClF,6, 23 2‐fluorooxirane,24 and (2,2‐ 2 H 2 )thiirane‐1‐oxide 25, 26…”

Section: The Most Relevant Parameters P̃0 P̃1 P̃2 [10−15 Cm−1] Obtamentioning

confidence: 99%

Parity Violation in Fluorooxirane

Berger

Qüack

Stohner

2001

Angew. Chem. Int. Ed.

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Dedicated to Professor Paul von RagueÂ Schleyer on the occasion of his 70th birthdayVant Hoff pointed out more than a century ago [1] that the heat of formation and the entropy of enantiomers of chiral molecules must be exactly equal for symmetry reasons. Traditional quantum chemistry which only includes the electromagnetic interaction finds just this symmetry. [2] However, electroweak quantum chemistry which includes parity violation predicts an energy and entropy difference. One of the greatest challenges in the current understanding of fundamental aspects of the structure and dynamics of chiral molecules concerns the experimental proof of the role of parity violation because of the weak nuclear interaction. [3] Experimental spectroscopic approaches have been proposed for some time. One of these approaches is to measure directly the heat of reaction D r H 0 0 for the transformation of S into R enantiomers which is related to the parity violating energy difference D pv E [3,4] as shown in Equation (1).Another approach is measuring certain frequency shifts of the enantiomers, for instance in NMR, [5] microwave, [6] IR, [6±10] or Möûbauer [11] spectra of R and S enantiomers (see the diagram in Figure 1).The recent theoretical discovery [12,13] that parity-violating effects in chiral molecules are typically one to two orders of magnitude larger than previously anticipated [14,15] has stimulated intensified theoretical [16±22] and experimental interest [6,10,11] in this field. Of particular importance are experi-0.17 mmol, 94 %). No PPN resonances were observed by 1 H NMR spectroscopy. UV/VIS (MeCN): l (e) 210 (6.8 Â 10 4 ), 233 (2.1 Â 10 4 ), 260 nm (6 Â 10 3 ).[PPN]-2: To a solution of Na[PPN]-2 (100 mg, 0.050 mmol) in warm ethanol (10 mL) was added a solution of FeCl 3´6 H 2 O (14 mg, 0.050 mmol) in ethanol (5 mL). The purple reaction solution was stirred for 30 min at 25 8C and then kept at À 18 8C for 3 h. Dark purple crystals precipitated which were separated by filtration, recrystallized from ethanol, and dried (m.p. 197 8C) to yield [PPN]-2 (90 mg, 0.046 mmol, 90 %). Electrospray MS (MeCN), negative-ion mode: m/z (%): 1416.0 (100) [2] À ; VIS (MeCN): l (e) 537 nm (1.4 Â 10 4 ); EPR (solid, 273 K): g 2.1997. 2: A sample of K 2 -2 (100 mg, 0.067 mmol) was dissolved in ethanol (10 mL) and a solution of FeCl 3´6 H 2 O (45 mg, 0.166 mmol) in ethanol (5 mL) was added. The reaction mixture turned purple and then dark red. The suspension was stirred for 1 h at room temperature and the precipitate was removed by filtration. The orange-brown solid was recrystallized from ethanol (m.p. 155 8C) to give 2 (80 mg, 0.057 mmol) in 84 % yield. FAB-MS (acetone), negative-ion mode: m/z (%): 1324.7 (25) [2 À CH 2 Ph] À , 1415.8 (100) [2] À , 1506.7 (70) [2CH 2 Ph] À ; 11 B NMR (160 MHz, acetone): d 43.3 (s); VIS (MeCN): l (e) 467 nm (1.7 Â 10 4 ). [8] In neutral, zwitterionic species such as closo-B 12 H 10 (SMe 2 ) 2 the B 12 cluster retains 26 skeletal electrons and thus two negative charges are delocalized throughout th...

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The Synthesis of [2-2H1]Thiirane-1-oxide and [2,2-2H2]Thiirane-1-oxide and the Diastereoselective Infrared Laser Chemistry of [2-2H1]Thiirane-1-oxide

Cited by 17 publications

References 25 publications

High‐Resolution Fourier Transform Infrared Spectroscopy

High‐Resolution Fourier Transform Infrared Spectroscopy

Paritätsverletzung in Fluoroxiran

Parity Violation in Fluorooxirane

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