The Common Chlorine Nuclear Electric Quadrupole Coupling Tensor for Acyl Chlorides R. A. Powoski and S. A. Cooke.

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The Common Chlorine Nuclear Electric Quadrupole Coupling Tensor for Acyl Chlorides R. A. Powoski and S. A. Cooke

We have recently recorded and analyzed the rotational spectra of several acyl chlorides. NF 3F 4F PF G. S. Grubbs II, R. A. Powoski, D. Jojola and S. A. Cooke J. Phys. Chem. A 114, (2010). R. A. Powoski, W. C. Bailey, and S. A. Cooke. J. Mol. Spectrosc. 273, 1-5 (2012).

We have recently recorded and analyzed the rotational spectra of several acyl chlorides. G. S. Grubbs II, C. T. Dewberry, K. C. Etchison, M. M. Serafin, S. A. Peebles and S. A. Cooke J. Mol. Spectrosc. 242, (2008).

C-3 C-4 We have recently recorded and analyzed the rotational spectra of several acyl chlorides. R. A. Powoski, G. S. Grubbs II and S. A. Cooke J. Mol. Struct. 963, (2010).

C-4 summary:

C-5 summary: E = 0.0 kJ / mol E = 1.5 kJ / mol

“A Search Accelerated Correct Intensity Fourier Transform Microwave Spectrometer with Pulsed Laser Ablation Source.” G. S. Grubbs II, C. T. Dewberry, K. C. Etchison, K. Kerr and S. A. Cooke Rev.Sci. Instrum. 78, (2007).Rev.Sci. Instrum. 78, (2007).

Spectroscopic parameters for two conformers of pentanoyl chloride R. A. Powoski and S. A. Cooke. J. Mol. Struct. 1021, (2012).

Comments on acyl chloride lowest energy conformers: 1.The O=CCC torsional angle appears to always be 0 o. 2.In regards to the first CCCC torsional angle the 180 o and 70 o conformers are almost degenerate. (Stiff competition between steric effects and the stabilizing “gauche effect”?). 3.Initial evidence suggests the second CCCC torsional angle prefers 180 o.

The Cl nuclear quadrupole coupling tensor in the principal axes systems for a selection of acyl chlorides

R H -C(=O)Cl eQq zz (Cl) = -59(1) MHz R F -C(=O)Cl eQq zz (Cl) = -65(1) MHz Common values:

eQq zz (Cl) in MHz Methyl chloride, CH 3 Cl (11) Ethyl Chloride, CH 3 CH 2 Cl Trans - Propyl Chloride, CH 3 CH 2 CH 2 Cl (11) Trans-Trans – Butyl Chloride CH 3 CH 2 CH 2 CH 2 Cl G.Wlodarczak, D.Boucher, R.Bocquet, and J.Demaison, J.Mol. Spectrosc. 116,251(1986). M.Hayashi and T.Inagusa, J.Mol.Struct. 220,103(1990). A.de Luis, M.E.Sanz, F.J.Lorenzo, J.C.López, and J.L.Alonso, J.Mol.Spectrosc. 184,60(1997). S.Melandri, P.G.Favero, D.Damiani, W.Caminati, and L.B.Favero, J.Chem.Soc. Faraday Trans. 90,2183(1994). Normal Alkyl Chlorides R H -Cl eQq zz (Cl) = -70(2) MHz

eQq zz (N) in MHz Methyl Cyanide, CH 3 CN (98) Ethyl Cyanide, CH 3 CH 2 CN Trans - Propyl Cyanide, CH 3 CH 2 CH 2 CN (44) Trans-Trans – Butyl Cyanide CH 3 CH 2 CH 2 CH 2 CN (25) M.Simeckova, S.Urban, U.Fuchs, F.Lewen, G.Winnewisser, I.Morino, and K.M.T. Yamada, J.Mol.Spectrosc. 226,123(2004). H.M.Heise, H.Lutz, and H.Dreizler, Z.Naturforsch. 29a,1345 (1974); H.Mäder, H.M.Heise, and H.Dreizler, Z.Naturforsch. 29a,164 (1973). J.Demaison and H.Dreizler, Z.Naturforsch. 37a,199(1982). R.K.Bohn, J.L.Pardus, J.August, T.Brupbacher, and W.Jäger, J.Mol.Struct ,293(1997). Normal Alkyl Cyanides R H -CN eQq zz (N) = -4.2(1) MHz

IUPAC, Project No We propose to collect relevant data and produce a table of “common” NQCC for appropriate nuclei in functionalized hydrocarbons. Raw data collected into a web resource. Summary information collected into an article. Why do this? 1.Provide a perspective. 2.Catch omissions and anomalies. 3.Tool for unknown spectra identification. 4.…?

Acknowledgements: Laboratory funding from the NSF IUPAC task group members: Bill Bailey Yoshiyuki Kawashima Zbigniew Kisiel Cristina Puzzarini

THE COMMON CHLORINE NUCLEAR ELECTRIC QUADRUPOLE COUPLING TENSOR FOR ACYL CHLORIDES R. A. POWOSKI, Glori Energy, Inc., 4315 South Dr, Houston, Texas 77053; S. A. COOKE, School of Natural and Social Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY We have determined the complete 35 Cl and 37 Cl nuclear electric quadrupole coupling tensors for two conformers of valeroyl chloride, CH 3 -(CH 2 ) 3 -COCl, using pure rotational spectroscopy. These tensors have been diagonalized into the principal axes and compared with chlorine principal quadrupole coupling tensors for a number of simple acyl chlorides. In general the components of the chlorine principal quadrupole coupling tensor, and in particular zz, are invariant to the organic group attached to the acyl chloride. It is evident, and not surprising, that the carbonyl of the acyl chloride functional group dominates the electric eld gradient at the chlorine nucleus. We have found a common, acyl chloride functional group, 35 Cl  zz value of -59(1) MHz. These findings will be discussed along with other work on tabulating common principal nuclear electric quadrupole coupling constants for relevant nuclei in simple organic functional groups. This work supported by IUPAC, Project No