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Mass-Analyzed Threshold Ionization Spectroscopy

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1 Mass-Analyzed Threshold Ionization Spectroscopy
Yttrium-Assisted C-H and C-C Bond Activation of Ethylene (C2H4) Probed by Mass-Analyzed Threshold Ionization Spectroscopy Jong Hyun Kim, Dong-Sheng Yang June 23th 2016 International Symposium on Molecular Spectroscopy Champaign-Urbana, Illinois

2 Introduction Metal activation of hydrocarbons plays an important role in organic synthesis and catalysis Understanding of metal mediated C-H & C-C activation helps to figure out the reaction mechanisms of metal-hydrocarbon reactions Few spectroscopic studies, little information about the structures and electronic states of the intermediates and products.

3 La + Ethylene  La(C2H2) + La(C4H6)
Background La + Ethylene  La(C2H2) + La(C4H6) La([Xe]5d16s2) vs. Y([Kr]4d15s2) Similar electron configurations, but different promotion energies What about Yttrium + Ethylene reaction? Similar or different? La La C2V CS Kumari, Sudesh Electron and ion spectroscopy of metal hydrocarbon complexes. Ph.D. dissertation, University of Kentucky

4 Wiley-McLaren Time-of-Flight Mass Spec.
Experimental Setup Wiley-McLaren Time-of-Flight Mass Spec. MCP Detector Electric Field (200 V/cm) Extraction Can Pulse Valve GV He Pulse Field Ionization 240 V/cm UV 42800 – cm-1 (0.45 – 0.15 mJ/pulse) 532 nm < 2.0 mJ/pulse Diffusion Pump Turbo Pump Reaction Chamber Spectroscopy Chamber

5 TOF Mass Spectrum of La vs. Y + Ethylene
Kumari, Sudesh, Electron and Ion Spectroscopy of Metal Hydrocarbon Complexes. Ph.D. dissertation, University of Kentucky

6 PIE Curve of Y(C2H2) Due to the Y atomic transition

7 Experimental and Simulated Spectra
45679 / 45586 536 / 530 ~ 45 576 / 565 830 / 821 / 1386 Experimental 1A1  2A1 250 K 25 cm-1 FWHM 1A1  2A1 5 K 25 cm-1 FWHM

8 AIE and Vibrational Frequencies (cm-1)
Y(C2H2), C2v isomer MATI BPW91 AIE: 1A1 ¬ 2A1 45679 45586 Assignment n 𝟑 + 830 821 n 𝟒 + 576 565

9 Geometries (C2V) Neutral Cation Y Y 2A1 1A1 2.208 2.159 1.355 1.355
C-C : 1.54 C=C : 1.34 Unit: Å 2A1 Kumari, Sudesh, Electron and Ion Spectroscopy of Metal Hydrocarbon Complexes. Ph.D. dissertation, University of Kentucky

10 TOF Mass Spectrum of La vs. Y + Ethylene
Kumari, Sudesh, Electron and Ion Spectroscopy of Metal Hydrocarbon Complexes. Ph.D. dissertation, University of Kentucky

11 PIE Curve of Y(C2H4) Due to the Y atomic transition

12 Experimental and Simulated Spectra
45603 / 45681 ~ 77 444 / 452 784 / 833 X 610 / 659 (330): A1  A2  A2 = A1 totally symmetric A1  A2 = A2 Experimental 1A1  2A1 250 K 25 cm-1 FWHM 1A1  2A1 5 K 25 cm-1 FWHM

13 AIE and Vibrational Frequencies (cm-1)
Y(C2H4), C2v isomer MATI BPW91 AIE: 1A1 ¬ 2A1 45603 45681 Assignment n 𝟒 + 784 833 n 𝟓 + 444 452 Not Measured (610) n 𝟖 + 330 (659)

14 Geometries (C2V) Neutral Cation Y Y 2A1 1A1 La(C2H4): Not detected
2.264 2.214 1.526 1.521 2A1 1A1 C-C : 1.54 C=C : 1.34 Unit: Å

15 TOF Mass Spectrum of La vs. Y + Ethylene

16 PIE Curve of Y(C4H6) Thermally excited

17 Experimental and Simulated Spectra
43475 / 43014 308 / 280 352 / 328 392 / 387 ~26 424 / 422 504 / 524 Experimental 1A’  2A’ 200 K 25 cm-1 FWHM 1A’  2A’ 5 K 25 cm-1 FWHM

18 Experimental and Simulated Spectra
43473 / 43014 422 / 422 350 / 328 502 / 524 400 / 387 310 / 280 492 / 498 798 / 794 ~ 26 102 10X Experimental 1A’  2A’ 200 K 25 cm-1 FWHM 1A’  2A’ 5 K 25 cm-1 FWHM

19 AIE and Vibrational Frequencies (cm-1)
Y(C4H6), CS isomer MATI BPW91 AIE: 1A' ¬ 2A' 43473 43014 Assignment n 𝟏𝟏 + 502 524 n 𝟏𝟐 + 422 422 n 𝟏𝟑 + 350 328

20 Geometries (CS) Neutral Cation Y Y 4 4 2 3 2 3 2A’ 1A’ 1 1 2.329 2.394
2.549 2.479 1 4 1 4 122.68° 124.28° 1.456 2 1.454 3 2 3 1.397 1.402 2A’ 1A’ C-C : 1.54 C=C : 1.34 Unit: Å Kumari, Sudesh, Electron and Ion Spectroscopy of Metal Hydrocarbon Complexes. Ph.D. dissertation, University of Kentucky

21 Conclusions Y + ethylene reaction produced Y(C2H2), Y(C2H4), and Y(C4H6) via C-H activation and C-C coupling. Their structures, AIEs, electronic states, and vibrational modes were measured and investigated, respectively. Similar to La + ethylene reaction, except for one more product, Y(C2H4). This may be caused by different nd1(n+1)s2  nd2(n+1)s1 promotion energies.

22 Thank you Any Questions?

23

24 excited state: 5d2 6s1 2F 7011.909 cm-1 (20.048 kcal/mol)
*La promotion energy:  ground state: 5d1 6s2 2D 0 cm-1 excited state: 5d2  6s1 2F cm-1 ( kcal/mol) *Y promotion energy: ground state: 4d1 5s2 2D 0 cm-1 excited state: 4d2 5s1 2F cm-1 ( kcal/mol) (1cm-1 = kcal/mol) As we guessed, La has lower promotion energy than Y. Weisshaar, Bare Transition Metal Atoms in the Gas Phase: Reactions of M, M+, and M2+ with Hydrocarbons, Acc. Chem. Res. 26, 213 (1993)

25 Time-of-Flight Mass Spectrum of La + Ethylene

26 Time-of-Flight Mass Spectrum of Y + Ethylene

27 MATI Spectrum of Y(C4H6) 43475 308 352 392 ~26 424 504

28 Possible Structures? Y(C4H6)
A big energy difference between the calculated and experimental IE Disagreement between the simulated and experimental spectra A large structural change upon ionization  B was considered as the most likely candidate Hewage, Dilrukshi C Spectroscopic characterization of lanthanum-mediated hydrocarbon activation. Ph.D. dissertation, University of Kentucky

29 Possible Structures? Cs Electronic States Relative Energies (cm-1)
Geometry optimization and frequency calculations were carried at BPW91/ G** for C, H and LANL2DZ for Yttrium Electronic States Relative Energies (cm-1) 2A’ (neutral) 4A’’ (neutral) 10123 1A’ (ion) 43014 3A’’ (ion) 52670 IE (cm-1) 1A' ¬ 2A' IE (cm-1) 3A'' ¬ 4A'' 42547 IE (exp) = cm-1 3A’’  2A’, cm-1 (high energy) : omitted

30 Experimental and Simulated Spectra
43475 (0-0) Experimental 43014 1A’  2A’, 200 K, 25 cm-1 FWHM 42547 3A’’  4A’’, 200 K, 25 cm-1 FWHM 3A’’  2A’, cm-1 ( high energy) : omitted

31 Wiley-McLaren Time-of-Flight Mass Spec.
Metal Atom reaction? Wiley-McLaren Time-of-Flight Mass Spec. MCP Detector Electric Field Electric Field (200 V/cm) Extraction Can HC Pulse Valve GV He Pulse Field Ionization 240 V/cm UV 42800 – cm-1 532 nm Diffusion Pump Turbo Pump Reaction Chamber Spectroscopy Chamber

32 Metal Atom reaction?

33 Metal Atom reaction?

34 Metal Atom reaction?

35 Metal Atom reaction?

36

37 Metal Atom reaction? (Pre-mixture gas)

38 Metal Atom reaction?

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