1. Rotational spectroscopy of two telluric compounds : vinyl- and ethyl-tellurols R.A. MOTIYENKO, L. MARGULES, M. GOUBET Laboratoire PhLAM, CNRS UMR 8523, Université de Lille 1, 59655 Villeneuve d'Ascq Cedex, France H. MØLLENDAL Centre for Theoretical and Computational Chemistry (CTCC), University of Oslo, P.O. Box 1033, Blindern, NO-0315 Oslo, Norway J. C. GUILLEMIN Sciences Chimiques de Rennes-Ecole Nationale Supérieure de Chimie de Rennes-CNRS, 35700 Rennes, France

2. Chalcogens O, S and Se molecules are well studied Telluric molecules are potentially highly toxic and exhibit a low stability at room temperature (half life ≈ 60 min) Rotational spectra of telluric molecules are poorly studied (only H 2 Te molecule has been previously characterized by its microwave spectrum I.N. Kozin et al. J.Mol.Spec. 180, 402 – 413 2006) Objective : to determine physico-chemical properties of vynil and ethyl-tellurol Additional interest: are we able to predict reliable spectroscopic parameters for molecules containing Te using commercial programs like Gaussian? Synthesis: Quite recently new method has been developed : J. C. Guillemin, A.Bouayard, D.Vijaykumar, Chem. Commun., 1163-1164 (2000) R – Te – Te – R nBu 3 SnH –(nBu 3 SnSeH) R –TeH R = Et, CH2=CH

3. Ab initio structures method: MP2(full) for Te atom in order to account for relativistic effects small core pseudo- potential basis set is used: cc-pVTZ-PP, the size of the core: 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 for C atoms cc-pCVTZ basis set is used Ethyl-tellurol Vinyl-tellurol gauchesyn gauchetrans µ a =0.7 D µ b =0.3 D µ c =0.1 D µ a =0.6 D µ b =0.0 D µ c =0.0 D µ a =1.2 D µ b =0.3 D µ c =0.1 D µ a =1.2 D µ b =0.5 D µ c =0.0 D

4. Experiment Optimum sample temperature for experiment : 193 – 200 K. At higher temperatures the sample deteriorates very rapidly. Very slow flux in order to provide sufficient vapor pressure in absorbing cell and at the same time to evacuate decomposition products Frequency synthesizer Absorbing cell Detector to diffusion + rotary pump Sample at 193 – 198 K At room temperature measurements in Lille: 75 – 300 GHz measurements in Oslo: 30 – 70 GHz

5. Spectroscopy sample: vinyl-tellurol 25 GHz recorded in 2h with at 0.1MHz/point

6. Spectroscopy 130 Te (34%) 128 Te (31.7%) 126 Te (18.9%)

7. Spectroscopy predicted pattern a R 0,1 J=30←29

8. Spectroscopy J=28←27 J=29←28 J=30←29 J=31←30 f=(B+C)(J+1) B+C ≈ 5.58 GHz ethyl-tellurol 25984 5637 Vinyl-tellurol sample contains about 30 % of ethyl-tellurol! vinyl-tellurolassigned species A (MHz)4173325602 B+C (MHz)62215585

9. Ethyl-tellurol 0.8 MHz Are the doublets coming from internal rotation of methyl top? – No, calculated barrier height value is too high: V 3 >1000 cm -1 The most probable origin of the doublets is the tunneling between two equivalent gauche configurations

10. Ethyl-tellurol trans conformer has been also assigned calculated energy difference between trans and gauche conformations is in agreement with observed relative intensities gauche conformer is proved to be the most stable one problems in fitting both forms: gauche : Coriolis coupling between 0+ and 0-, wrms = 1.5 trans : probable interaction with v=1 of gauche??? ≈ 600 MHz 0+ 0-

11. Vinyl-tellurol Species 1Species2Species 3Species 4syngauche A (MHz) 415474125741032428784370941733 B (MHz) 318231783165313831613208 C (MHz) 297529842988292429483013 syn gauche Δ (amu A 2 )-1.13-1.87-2.810.02 species 2 species 1 species 3 14 1,13 – 13 1,12 both gauche and syn forms have been assigned syn conformer does not exhibit any complication in its spectrum: its isotopic species 130 Te, 128 Te, 126 Te and 125 Te have been fitted within experimental accuracy the lines associated with gauche conformer exhibit anomalies in their relative intensities (ω t =126 cm -1 )

12. Vinyl-tellurol complications found in interpretation of the observed spectrum of gauche conformer can be explained by large amplitude motion: TeH torsion

13. Summary of preliminary results Spectra of ethyl and vinyl tellurol have been recorded in the frequency range up to 300 GHz All stable conformations of both molecules have been assigned Doublets observed for gauche conformation of ethyl tellurol are associated with tunneling motion between two equivalent configurations