La-Mediated Bond Activation, Coupling, and Cyclization of 1,3-butadiene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry.

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Presentation transcript:

La-Mediated Bond Activation, Coupling, and Cyclization of 1,3-butadiene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry University of Kentucky Dilrukshi Hewage, Ruchira Silva and Dong-Sheng Yang 1

Motivation  Significant role in organic synthesis and catalysis  Many kinetic studies in the gas phase, but very few spectroscopic measurements  Identify structures and investigate reaction pathways  Benchmark to test theoretical models and to design tailored catalyst 2

Background C-C bond strength ≈ 348 kJmol -1 C-H bond strength ≈ 418 kJmol -1 C-C bond activation  Less common than C-H activation. Why?  C-C bonds are less abundant than C-H bonds  C-C bonds are highly directional. 3 Hinrichs, R. Z.; Schroden, J. J.; Davis, H. F. J. Phys. Chem. A 2008, 112, 3010 Siegbahn, P.E.M.; Blomberg, M.R.A. J. Am. Chem. Soc. 1992, 114, 10548

Previous Studies  Cross molecular beam studies on M + C n H n have revealed the product distribution and their energy distribution Ex: Y + C 2 H 2 → YC 2 + Y-C 2 H  Fast flow reactor methods have revealed the kinetics  Theoretical studies on reaction pathways Glendening, E. D. Journal of Physical Chemistry A 2004, 108, Porembski, M.; Weisshaar, J. C. Journal of Physical Chemistry A 2001, 105,

Spectroscopy Chamber Reaction Chamber ND:YAG(355 nm) ND:YAG (532 nm) Dye laser Frequency Doubling Electronics Diffusion Pump Turbo Pump Experimental Setup 5

6 Reaction chamber Spectroscopy chamber Piezo valve & Face plate Skimmer Diffusion pump Extraction Cans TOF MCP Turbo pump Micro motor Deflection plates

7 Extraction Cans TOF Tube MCP Detector Reaction Chamber Metal Rod Nozzle Laser(532 nm) Carrier Gas & Hydrocarbon Spectroscopy Chamber

8 Extraction Cans TOF Tube MCP Detector Source Chamber Spectroscopy Chamber UV ML + ML 320 V/cm

9 Extraction Cans TOF Tube MCP Detector Source Chamber UV MATI ions Promt ions MATI ions T=0 TOF spectrum Spectroscopy Chamber

Ion Neutral + UV laser 320 V/cm Rydberg states Extraction Can 1 ~ 5-20VDC 10

Theoretical Calculations  DFT-B3LYP for geometry optimization and frequency calculation La ([Xe] 6s 2 5d 1 ) : SDD (Stuttgart/Dresden relativistic effective core potential) C and H : G(d,p)  Spectral simulation Franck-Condon factors and Boltzmann distribution 11

La+1,3-butadiene 12

TOF-MS of 225nm Time / us Relative intensity La LaO LaC 2 LaC 2 H 2 LaC 4 H 4 LaC 4 H 2 LaC 4 H 6 LaC 6 H 8 LaC 6 H 6 13

TOF-MS of 225nm LaC 2 H 2 LaC 4 H 4 LaC 4 H 6 LaC 6 H 8 LaC 6 H 6 14 Liu, Y.; Kumari, S.; Roudjane, M.; Li, S.; Yang, D.-S. Journal of Chemical Physics 2012, 136,

PIE Spectra Wavenumber / cm -1 LaC 6 H 6 LaC 4 H 6 15

MATI of LaC 2 H

Experimental & Simulated Spectra 520 / / / / 814 IP= / A 1 ← 2 A 1, 200 K 17

LaC 4 H 6 Rel. Energy A B 18

Experimental MATI Spectrum & Simulation Wavenumber / cm -1 1 A' ← 2 A', A ← 2 A,

Wavenumber / cm -1 1 A' ← 2 200K (a) (b) (c) (a) (c) (b) 20 Experiment

Simulation / / / / IP / cm A’ ← 2 A’ 21

Geometry NeutralIon LaC LaC C1C2C1C C2C3C2C < C 1 LaC < LaC 1 H < LaC 1 C 2 H C3C3 C2C2 C1C1 C4C4 H1H1 H2H2 22

Geometry of the Complex Geometry parameter NeutralIon La-C La-C C1-C2C1-C C2-C3C2-C < C 1 LaC < LaC 1 H < LaC 1 C 2 H

Bonding of the Complex 24 C1C1 C2C2 C4C4 C3C3 C1C1 C2C2 C4C4 C3C3 C 1 -C 2 = C 3 -C 4 > C 2 -C 3 M-C 1 < M-C 2 C 1 -C 2 C 2 -C 3 La-C 1 La-C Diamond, G. M.; Green, M. L. H.; Walker, N. M.; Howard, J. A. K.; Mason, S. A. J. Chem. Soc. Dalton Trans. 1992, 2641 C 1 -C 2 = C 3 -C 4 < C 2 -C 3 M-C 1 > M-C 2 C1C1 C2C2 C3C3 C4C4 σ 2, π metallacyclopentene π 2 model Bond lengths are in Å

25 A B ethylene C 2 H 4 + La(C 2 H 2 ) - H 2 → B propene C 3 H 6 + LaCH 2 - H 2 → A + B 1-butene La+C 4 H 8 - H 2 → A + B 1,3-butadiene La+C 4 H 6 → B

TOF of 225nm LaC 2 H 2 LaC 4 H 4 LaC 4 H 6 LaC 6 H 8 LaC 6 H 6 26

MATI Spectrum of LaC 6 H 6 Wavenumber / cm -1 27

MATI & ZEKE Spectra of La-Benzene Liu, Y.; Kumari, S.; Roudjane, M.; Li, S.; Yang, D.-S. Journal of Chemical Physics 2012, 136, ZEKE MATI 28

ZEKE and Simulation of LaC 6 H 6 Liu, Y.; Kumari, S.; Roudjane, M.; Li, S.; Yang, D.-S. Journal of Chemical Physics 2012, 136,

La-Benzene E / cm -1 AIE41401 C-H wagging and in plane ring deformation of cation527 La + - benzene stretching295 Ring rocking39 30

~225 ~340 31

Summary LaC 2 H 2 LaC 4 H 4 LaC 4 H 6 LaC 6 H 8 LaC 6 H 6 32  Structures and electronic states of the products  Experimental ionization energies and vibrational frequencies

Thank you 33

HOMO LaC 2 H 2 LaC 4 H 6 LaC 6 H 6 34