OSU – June - 20061 STEPHEN KUKOLICH, Chemistry Dept., University of Arizona, MICHAEL PALMER School of Chemistry, University of Edinburgh, PETER GRONER,

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OSU – June STEPHEN KUKOLICH, Chemistry Dept., University of Arizona, MICHAEL PALMER School of Chemistry, University of Edinburgh, PETER GRONER, Chemistry, University of Missouri-Kansas City, and CHAKREE TANJAROON, Chemistry, University of Alberta, Experimental Rotational Spectra for MnRe(CO) 10 and o-C 6 H 4 † Required Accurate theoretical Calculations for Successful Analysis † Measured at Harvard with Pat Thaddeus and Mike McCarthy

OSU – June  Observing and Measuring the Rotational Transition Frequencies was Difficult  B = MHz ( 187 Re )  eQq( 187 Re) = (38) MHz  eQq( 55 Mn) = (5) MHz  Normal Isotopomer transitions were readily observed  13 C Isotopomer lines often obscured by other products of Discharge (Shotgun effect)

OSU – June MnRe(CO) 10 + > Symmetric top with C 4v symmetry -> Combination of small B-values with two quadrupoles resulted in congested and difficult-to-assign spectra (J=11 → 12 and 12→ 13 ) + > Michael Palmer and Martyn Guest (Edinburgh) calculated the eQq values sufficiently accurately to allow unambiguous assignments of the spectra

OSU – June Example Spectra for 8, and 10 MHz “pieces” of the spectrum

OSU – June Pair of measured transitions 2000 Shots

OSU – June  C 4v symmetry  Only K=4n transitions observed  Staggered or Eclipsed? † † F. A. Cotton, Austin 2004 (E) (S) xx

OSU – June

8 The structure of o – benzyne and vibrational averaging effects. Spectra Measured on HARVARD FTMWS 1 Discharge 0.5% BENZENE in NEON Normal Isotopomer - 27 b-dipole transitions 13 C b-dipole transitions D b-dipole transitions D b-dipole transitions 13 C 1 (1) - 10 b-dipole transitions 13 C 1 (3) - 9 b-dipole transitions 13 C 1 (5) - 10 b-dipole transitions 1. S. G. Kukolich, M. C. McCarthy and P. Thaddeus, J. Phys. Chem. 108, , (2004) DIFFICULT To MEASURE

OSU – June Search for 13 C lines… in a sea of lines from other radicals and molecules produced in the DISCHARGE. JUNK WRONG MOLECULE GOOD ONE kHz

OSU – June Least-squares structure fit  The inertial defect for the normal isotopomer of o-benzyne is  = I CC – I AA – I BB = (1) amu Å 2, consistent with a PLANAR STRUCTURE.  This value is sufficiently large that when trying to fit the measured A, B, and C rotational constants with a planar structure, some of the deviations will be as large as 1 MHz.  STANDARD DEVIATION FOR FIT = 1.05 MHz  Experimental errors are < 2 kHz! EXPTCALC.DEV. NORMAL A B C C1 A B C

OSU – June Least-squares fit to determine the structure  Most of the same vibrational averaging effects which contribute to the differences between the r 0 and r e coordinates, will also contribute to this inertial defect.  Problem 1. We are trying to fit a PLANAR, (r e ) structure to EXPERIMENTAL A, B, and C which have non-zero inertial defect,  (characteristic of the r 0 coordinates )  Problem 2. The r 0 coordinates are different for each of the measured isotopomers  SOLUTION: Find the  k, vibration-rotation constants, so we fit the r e structure,  same for all isotopomers

OSU – June VIBRATIONAL AVERAGING EFFECTS – RELATED TO VIBRATION-ROTATION INTERACTION CONSTANTS  k Values for these  k were calculated by Peter Groner 1, University of Missouri

OSU – June Final Structure of o-benzyne  r(C 1 -C 2 ) for HCCH =1.203 Å r(C 1 -C 2 ) for H 2 CCH 2 =1.332 Å Now the fit is MUCH improved (  < 30 kHz)  r(C 2 -C 3 ) for benzene = Å P. Groner and S. G. Kukolich, J. Mol. Struct , 178 (2006)  r(C 2 -C 3 ), NMR value → 1.24(2) Å Grant, Michl, et al.

OSU – June The r e structure of o-benzyne (Distances r in Å) Structural parameter rere MP2/ 6-31G(d) r s / Kraitch- man B3LYP/ 631G(d,p) BPW9 1/ cc- pVDZ Ref.This work [a][b][c] r(C 1 -C 2 )1.255(3) (8) r(C 2 -C 3 )1.383(2) (2) r(C 3 -C 4 )1.403(2) (2) r(C 4 -C 5 )1.405(3) (14) r(C 3 -H 1 )1.080(1) (2) r(C 4 -H 2 )1.082(1) (9) Benzene r(C-C) b (1)1.395 r(C-H) b (3)1.087 [ a]S. G. Kukolich, M. C. McCarthy, P. Thaddeus, J. Phys. Chem A 108 (2004) [b]S. G. Kukolich, C. Tanjaroon, M. C. McCarthy, P. Thaddeus, J. Chem. Phys. 119 (2003) [c]C. J. Cramer, Nash, J. J. and R. R. Squires, Chem. Phys. Lett. 277 (1997)

OSU – June Acknowledgements N$F - This material is based upon work supported by the National Science Foundation under Grant No. CHE This support from the National Science Foundation is gratefully acknowledged Willis Flygare and Terry Balle Harvard: Pat Thaddeus, Mike McCarthy Arizona: Kristen Keck Edingburgh: Martyn Guest, Phillip Camp Department of Chemistry, University of Arizona.

OSU – June

OSU – June Other isomers of benzyne The structural isomers of didehydrobenzene – ortho-benzyne, meta-benzyne and para-benzyne. Calculations show  H f  (o-benzyne) >  H f  (m- benzyne)>  H f  (p-benzyne)

OSU – June O - BENZYNE  Brown, Godfrey, Rodler, Robertson (1st microwave, no structure)  Pyrolyzed: pthalic anhydride, or ninhydrin, or benzocyclobutene-R(1986, 2003)  Lineberger, Squires, et al. (1998)- electron afinities, singlet triplet splittings & vibrational frequencies PRESENT WORK (2002…)  Discharge 0.5% BENZENE in NEON  HARVARD SPECTROMETER (Sabbatical)