G. S. Grubbs II, S. A. Cooke⧧, and Stewart E. Novick,

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Presentation transcript:

G. S. Grubbs II*, S. A. Cooke⧧, and Stewart E. Novick*, THE CHIRPED-PULSE FOURIER TRANSFORM MICROWAVE (CP-FTMW) SPECTRUM AND POTENTIAL ENERGY CALCULATIONS FOR AN AROMATIC CLAISEN REARRANGEMENT MOLECULE, ALLYL PHENYL ETHER G. S. Grubbs II*, S. A. Cooke⧧, and Stewart E. Novick*, *Department of Chemistry, Wesleyan University, 52 Lawn Ave., Middletown, CT 06459-0180. ⧧ School of Natural and Social Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY 10577

Claisen Rearrangement Allyl Phenyl Ether 2-Allylphenol Discovered by L. Claisen1 in 1912 3,3 sigmatropic rearrangement Structure and conformation are key to reaction

Allyl Phenyl Ether Theory Parameter Value (MHz) A 4539.7 B 631.8 C 567.2 Calculations ran at MP2/6-311G++(3d,2p) level1 Gaussian 09, Revision A.02, M. J. Frisch et al, Gaussian, Inc., Wallingford CT, 2009.

Experiment Chirped-Pulse FTMW experiment1 TC04: Dan Obenchain Chirped-Pulse FTMW experiment1 Linewidths ~80 kHz with 10 kHz uncertainty G. S. Grubbs II, R. A. Powoski, D. Jojola and S. A. Cooke. J. Phys. Chem. A 114(2010) 8009.

Results 7.7-14 GHz 3 Conformers assigned to date

Current Fits Parameter Conformer 1 Conformer 2 Conformer 3 Calculation A /MHz 1738.31180(84) 1414.21(27) 4566.3(17) 4539.7 B /MHz 676.51449(42) 459.5562(18) 629.1613(26) 631.8 C /MHz 640.12176(39) 438.4575(17) 564.6389(26) 567.2 𝛥J /kHz 0.0922(15) 0.0522(16) [0.0922] ---- 𝛥JK /kHz 0.2849(78) 0.2826(85) [0.2849] 𝛥K /kHz 0.200(51) -15.(129)* [0.200] δJ /kHz -0.00924(73) 0.0115(20) [-0.00924] δk /kHz -1.16(14) 0.66(78) [-1.16] RMS /kHz 4.9 9.0 66 N 68 48 25 SPFIT/SPCAT: H. M. Pickett, J. Mol. Spectrosc. 148 (1991) 371 AABS Package : Z. Kisiel, L. Pszczolkowski, I. R. Medvedev, M. Winnewisser, F. C. D. Lucia, C. E. Herbst, J. Mol. Spectrosc. 233 (2005) 231.

2-Allylphenol Theory Calculations ran at MP2/6-311G++(3d,2p) level1 Parameter Value (MHz) A 2511.4 B 1008.0 C 795.4 Parameter Conformer 1 Conformer 2 A /MHz 1738.31180(84) 1414.21(27) B /MHz 676.51449(42) 459.5562(18) C /MHz 640.12176(39) 438.4575(17) Calculations ran at MP2/6-311G++(3d,2p) level1 Gaussian 09, Revision A.02, M. J. Frisch et al, Gaussian, Inc., Wallingford CT, 2009.

Potential Energy Scans Parameter Freq. (MHz) A 4624.7 B 626.9 C 560.7 Parameter Freq. (MHz) A 4194.7 B 693.1 C 597.1

Potential Energy Scans Parameter Freq. (MHz) A 2949.3 B 817.3 C 691.8 Parameter Freq. (MHz) A 3280.9 B 771.3 C 681.3 Double Rotation Still Running at Moment

Useful CP-FTMW Experiments Heated Nozzle Waveguide experiment where temperature can be varied

Conclusions Rotational spectrum of allyl phenyl ether has been observed and presented 3 Conformers of allyl phenyl ether assigned to date with a match to a structure Claisen rearrangement molecule 2-Allylphenol tested, but no match Other potential energy conformers do not match experimental values to date

And Now for Something Completely Different… Calculation APFD/ECP10MDF & aug-cc-pVQZ Bond Bond Distance (Å) Cu-F 1.74 H2 C.O.M-Cu 1.51 Notable Values eQq (MHz) Reference Monomer 63Cu-F 21.95(10) 1 H2- 63CuF 61.273(7) This Work Calculated De 105 kJ/mol 63Cu eQq H2-CuF ~ 3 x (63Cu eQq Monomer) CHEMICAL BOND! Hoeft et al., Z. Naturforsch., 25 a(1970), 35.

Acknowledgements NSF CHE-1011214 and US DOE for $$$ Daniel J. Frohman for some H2-CuF measurements and all calculations

Congratulations, Pete! Retired at the end of this year from Wesleyan We wish him well!!!