Six-fold-symmetry internal rotation in toluenes: the low barrier challenge of 2,6- and 3,5-difluorotoluene

Literature Information

Publication Date 2015-09-22
DOI 10.1039/C5CP03751D
Impact Factor 3.676
Authors

K. P. Rajappan Nair, Michaela K. Jahn, Alberto Lesarri, Vadim V. Ilyushin, Jens-Uwe Grabow


View Original

Abstract

Pure six-fold symmetry (V6) internal rotation poses significant challenges to experimental and theoretical determination, as the very low torsional barriers result in huge tunneling splittings difficult to identify and to model. Here we resolved the methyl group internal rotation dynamics of 2,6- and 3,5-difluorotoluene using a newly developed computer code especially adapted to V6 problems. The jet-cooled rotational spectra of the title molecules in the 5–25 GHz region revealed internal rotation tunneling doublings of up to 3.6 GHz, which translated in methyl group potential barriers of V6 = 0.14872(24) and 0.0856(10) kJ mol−1, respectively, in the vibrational ground-state. Additional information on Stark effects and carbon isotopic species in natural abundance provided structural data and the electric dipole moments for both molecules. Ab initio calculations at the MP2 level do not reproduce the tiny torsional barriers, calling for experiments on other systems and additional theoretical models.

Related Literature

Reagent-controlled regiodivergence in the [3,3]-sigmatropic rearrangement of N-(acyloxy)enamides

Norihiko Takeda, Narumi Arisawa, Misaki Miyamoto, Yukiko Kobori, Tetsuro Shinada, Masafumi Ueda

2019-09-27 Research Article

DOI: 10.1039/C9QO01109A

Recent advances in intramolecular C–O/C–N/C–S bond formation via C–H functionalization

Paran J. Borpatra, Bhaskar Deka, Mohit L. Deb, Pranjal K. Baruah

2019-09-10 Review Article

DOI: 10.1039/C9QO00863B

Commiphorines A and B, unprecedented sesquiterpenoid dimers from Resina Commiphora with striking activities on anti-inflammation and lipogenesis inhibition

Da-Peng Qin, Qian-Qian Di, Ying Liu, Wei-Lin Chen, Shu-Mei Wang, Yong-Xian Cheng

2019-10-09 Research Article

DOI: 10.1039/C9QO01046G

Constructing bridged multifunctional calixarenes by intramolecular indole coupling

Boris Bolshchikov, Sergey Volkov, Daria Sokolova, Alexander Gorbunov, Alina Serebryannikova, Igor Gloriozov, Dmitry Cheshkov, Stanislav Bezzubov, Wen-Sheng Chung, Vladimir Kovalev, Ivan Vatsouro

2019-08-13 Research Article

DOI: 10.1039/C9QO00859D

Thiol substrate-promoted dehydrogenative cyclization of arylmethyl thiols with ortho-substituted amines: a universal approach to heteroaromatic compounds

Mengjun Qiao, Ling Chen, Yibo Dong, Chengkang Jiao, Shengqi Liao

2019-06-15 Research Article

DOI: 10.1039/C9QO00554D

Synthesis of 1-naphthols via Cp*Co(iii)-catalyzed C–H activation and cyclization of sulfoxonium ylides with alkynes

Yongqi Yu, Qianlong Wu, Da Liu, Lin Yu, Ze Tan, Gangguo Zhu

2019-10-12 Research Article

DOI: 10.1039/C9QO00994A

Contents list

Front/Back Matter

DOI: 10.1039/C9QO90101A

1,3-Dipolar cycloaddition of nitrones to oxa(aza)bicyclic alkenes

Yongqi Yao, Wen Yang, Qifu Lin, Weitao Yang, Huanyong Li, Lin Wang, Fenglong Gu, Dingqiao Yang

2019-08-15 Research Article

DOI: 10.1039/C9QO00660E

Platinum(ii)-catalyzed dehydrative C3-benzylation of electron-deficient indoles with benzyl alcohols

Hidemasa Hikawa, Yuuki Matsuura, Shoko Kikkawa, Isao Azumaya

2019-07-17 Research Article

DOI: 10.1039/C9QO00831D

Front cover

Cover

DOI: 10.1039/C9QO90092F

You might also like

Compound Q&A

Is 6-(3-Fluorophenyl)picolinic acid (CAS: 887982-40-3) safe?

6-(3-Fluorophenyl)picolinic acid is generally considered safe for laboratory use...

887982-40-36-(3-Fluorophenyl)pi...
Compound Q&A

What industries use (3R)-3-Pyrrolidinol (CAS: 2799-21-5)?

(3R)-3-Pyrrolidinol is used in the pharmaceutical industry as a precursor for dr...

2799-21-5(3R)-3-Pyrrolidinol
Compound Q&A

What precautions should be taken when handling (4R,5R)-4,5-Diethoxycarbonyl-2,2-dimethyldioxolane (CAS: 59779-75-8)?

When handling (4R,5R)-4,5-Diethoxycarbonyl-2,2-dimethyldioxolane (CAS: 59779-75-...

59779-75-8(4R,5R)-4,5-Diethoxy...
Compound Q&A

How is 1-(6-Chloroimidazo[1,2-b]pyridazin-3-yl)ethanone (CAS: 90734-71-7) typically synthesized?

1-(6-Chloroimidazo[1,2-b]pyridazin-3-yl)ethanone is often synthesized via a mult...

90734-71-71-(6-Chloroimidazo[1...
Compound Q&A

What is the market or research trend for N-Ethyl-3,4-dimethylbenzylamine (CAS: 39180-83-1)?

The market for N-Ethyl-3,4-dimethylbenzylamine (CAS: 39180-83-1) remains steady,...

39180-83-1N-Ethyl-3,4-dimethyl...
Compound Q&A

What is Tert-butyl 3-(pyrrolidin-1-yl)azetidine-1-carboxylate (CAS: 1019008-21-9)?

Tert-butyl 3-(pyrrolidin-1-yl)azetidine-1-carboxylate is a chemical compound wit...

1019008-21-9Tert-butyl 3-(pyrrol...
Compound Q&A

What regulatory guidelines apply to 1-Bromo-3-chloro-2,4-dimethoxybenzene (CAS: 1228956-93-1)?

1-Bromo-3-chloro-2,4-dimethoxybenzene (CAS: 1228956-93-1) falls under the classi...

1228956-93-11-Bromo-3-chloro-2,4...
Compound Q&A

Is 8-Bromo-2-methyl-3,4-dihydroisoquinolin-1(2H)-one (CAS: 1368622-07-4) safe?

The safety of 8-Bromo-2-methyl-3,4-dihydroisoquinolin-1(2H)-one (CAS: 1368622-07...

1368622-07-48-Bromo-2-methyl-3,4...
Compound Q&A

Is Benzyl [(3S)-2,6-dioxo-3-piperidinyl]carbamate (CAS: 22785-43-9) safe?

Benzyl [(3S)-2,6-dioxo-3-piperidinyl]carbamate is generally safe when handled wi...

22785-43-9Benzyl [(3S)-2,6-dio...
Compound Q&A

How should 1-{[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]sulfonyl}pyrrolidine (CAS: 928657-21-0) be stored?

1-{[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]sulfonyl}pyrrolidine s...

928657-21-01-{[4-(4,4,5,5-Tetra...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.