Microwave and Quantum Chemical Study of Propargyl Selenocyanate (HC≡CCH<sub>2</sub>SeC≡N)

Møllendal, Harald; Konovalov, Alexey; Guillemin, Jean‐Claude

doi:10.1021/jp810810f

Cited by 3 publications

(2 citation statements)

References 20 publications

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“…25 No similar experimental information appears to be available for the oxygen member (HCtCCH 2 OCtN) of this series of cyanates.…”

Section: Discussionmentioning

confidence: 99%

“…The present conformational findings for HCtCCH 2 SCtN resemble the results for the selenium analogue, HCtCCH 2 SeCtN, where a conformation similar to ap was identified in the MW spectrum and is presumed to be the more stable form of the molecule. 25 No similar experimental information appears to be available for the oxygen member (HCtCCH 2 OCtN) of this series of cyanates.…”

Section: Discussionmentioning

confidence: 99%

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Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)

Møllendal

Guillemin

2010

J. Phys. Chem. A

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The MW spectrum of propargyl thiocyanate (HC[triple bond]CCH(2)SC[triple bond]N) has been investigated for the first time in the 25-80 GHz spectral region at room temperature or at 0 degrees C. The spectra of the ground vibrational state and of the first excited state of the C-S torsional vibration have been assigned for one conformer. This rotamer, denoted ap, has a symmetry plane (C(s) symmetry) and an antiperiplanar arrangement for the C-C-S-C link of atoms. It has previously been claimed that a conformer that has a synclinal conformation for this chain of atoms is present in the gas in approximately the same concentration as ap (approximately 50% of the gas), but this is not supported by the present experiments, where it is shown that the synclinal rotamer, denoted sc, cannot be present in a concentration exceeding 1/3 of the total. It is therefore concluded that ap must be at least 3.0 kJ/mol more stable than sc. The spectroscopic work has been augmented by quantum chemical calculations at advanced B3LYP/aug-cc-pVQZ, B3LYP/6-311++G(3df,3pd), and MP2/aug-cc-pVTZ levels of theory. These theoretical calculations underestimate the energy difference between ap and sc and predict values for the conformationally important C-C-S-C dihedral angle of the hypothetical synclinal form that deviates by approximately 10 degrees.

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“…25 No similar experimental information appears to be available for the oxygen member (HCtCCH 2 OCtN) of this series of cyanates.…”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)

Møllendal

Guillemin

2010

J. Phys. Chem. A

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Organic Selenocyanates, Tellurocyanates and Related Compounds

Toshimitsu¹

2013

Patai's Chemistry of Functional Groups

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Preparations, physical properties and reactions of organic selenocyanates, isoselenocyanates, and tellurocyanates are described. The preparations of organic selenocyanates include synthetic procedures (1) by substitution of halogen and related group, (2) from diazonium salts, (3) from organometallic compounds, (4) by selenocyanation, and (5) by formation of an SeCN bond. The preparations of organic isoselenocyanates include synthetic procedures (1) by formation of a CSe bond, (2) by substitution of halogen atom and (3) by [3.3]sigmatropic rearrangement. The reactions of organic selenocyanates include (1) additions to the CN bond, (2) substitution of the CN group, (3) elimination of the CN group, and (4) isomerization to isoselenocyanates. The reactions of organic isoselenocyanates include (1) addition of nitrogen nucleophile, (2) addition of oxygen nucleophile, (3) addition of sulfur, selenium or tellurium nucleophile, and (4) reaction of carbon nucleophile. Coverage of the literature is nearly complete from 1986 to 2011.

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Equilibrium structures of selenium compounds: The torsionally flexible molecule of selenophenol

Saragi

Juanes

et al. 2023

The Journal of Chemical Physics

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The equilibrium structure of selenophenol has been investigated using rotational spectroscopy and high-level quantum mechanical calculations, offering electronic and structural insight into the scarcely studied selenium compounds. The jet-cooled broadband microwave spectrum was measured in the 2–8 GHz cm-wave region using broadband (chirped-pulse) fast-passage techniques. Additional measurements up to 18 GHz used narrow-band impulse excitation. Spectral signatures were obtained for six isotopic species of selenium (80Se, 78Se, 76Se, 82Se, 77Se, and 74Se), together with different monosubstituted 13C species. The (unsplit) rotational transitions associated with the non-inverting μa-dipole selection rules could be partially reproduced with a semirigid rotor model. However, the internal rotation barrier of the selenol group splits the vibrational ground state into two subtorsional levels, doubling the dipole-inverting μb transitions. The simulation of the double-minimum internal rotation gives a very low barrier height (B3PW91: 42 cm−1), much smaller than for thiophenol (277 cm−1). A monodimensional Hamiltonian then predicts a huge vibrational separation of 72.2 GHz, justifying the non-observation of μb transitions in our frequency range. The experimental rotational parameters were compared with different MP2 and density functional theory calculations. The equilibrium structure was determined using several high-level ab initio calculations. A final Born–Oppenheimer (reBO) structure was obtained at the coupled-cluster CCSD(T)_ae/cc-wCVTZ level of theory, including small corrections for the wCVTZ → wCVQZ basis set enlargement calculated at the MP2 level. The mass-dependent method with predicates was used to produce an alternative rm(2) structure. The comparison between the two methods confirms the high accuracy of the reBO structure and offers information on other chalcogen-containing molecules.

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Microwave and Quantum Chemical Study of Propargyl Selenocyanate (HC≡CCH₂SeC≡N)

Cited by 3 publications

References 20 publications

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)

Organic Selenocyanates, Tellurocyanates and Related Compounds

Equilibrium structures of selenium compounds: The torsionally flexible molecule of selenophenol

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Microwave and Quantum Chemical Study of Propargyl Selenocyanate (HC≡CCH2SeC≡N)

Cited by 3 publications

References 20 publications

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH2SC≡N)

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH2SC≡N)

Organic Selenocyanates, Tellurocyanates and Related Compounds

Equilibrium structures of selenium compounds: The torsionally flexible molecule of selenophenol

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Product

Resources

About

Microwave and Quantum Chemical Study of Propargyl Selenocyanate (HC≡CCH₂SeC≡N)

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)

Microwave and Quantum Chemical Study of Propargyl Thiocyanate (HC≡CCH₂SC≡N)