1. 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
⧧ School of Natural and Social Sciences, Purchase College SUNY, 735 Anderson Hill Road, Purchase, NY 10577

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

3. 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.

4. 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.

5. Results
GHz
3 Conformers assigned to date

6. Current Fits Parameter Conformer 1 Conformer 2 Conformer 3 Calculation
A /MHz
(84)
(27)
4566.3(17)
4539.7
B /MHz
(42)
(18)
(26)
631.8
C /MHz
(39)
(17)
(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
(73)
0.0115(20)
[ ]
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.

7. 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
(84)
(27)
B /MHz
(42)
(18)
C /MHz
(39)
(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.

8. 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

9. 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

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

11. 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

12. 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.

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

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