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C-H Bond Activation of Butenes

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1 C-H Bond Activation of Butenes
Spectroscopic Identification of Y(C4H6) Isomers formed by Yttrium-Mediated C-H Bond Activation of Butenes Jong Hyun Kim, Dong-Sheng Yang June 20th 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 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 (both CS and C3V isomers were detected) La + isobutene  La(C4H6)
Background La + 1-butene  La(C4H6) (both CS and C3V isomers were detected) La + isobutene  La(C4H6) (only C3V isomer was detected) La([Xe]5d16s2) vs. Y([Kr]4d15s2) What about Y + Butene reactions? Similar or different? La La Hewage, Dilrukshi C Spectroscopic characterization of lanthanum-mediated hydrocarbon activation. 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 (0.45 – 0.15 mJ/pulse) 532 nm (< 2 mJ/pulse) Diffusion Pump Turbo Pump Reaction Chamber Spectroscopy Chamber

5 TOF Mass Spectrum of Y + 1-Butene Reaction

6 PIE Curve of m/z 143, Y(C4H6) Thermally excited

7 MATI Spectrum of Y(C4H6) 43473 ~26 422 400 350 310 492 3X 502 102 798 Compare to electronic structure calculations and spectral simulations to identify its structures & electronic states

8 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 most likely candidate Hewage, Dilrukshi C Spectroscopic characterization of lanthanum-mediated hydrocarbon activation. Ph.D. dissertation, University of Kentucky

9 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 (expt) = cm-1 3A’’  2A’, cm-1 (high energy)

10 Experimental and Simulated spectra
43473 (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)

11 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

12 AIE and Vibrational Frequencies (cm-1)
Y(C4H6), CS isomer MATI BPW91 AIE: 1A' ¬ 2A' 43473 43014 Assignment n 𝟏𝟎 + 798 794 n 𝟏𝟏 + 502 524 n 𝟏𝟐 + 422 422 n 𝟏𝟑 + 350 328

13 Geometries (CS) Neutral Cation Y Y 4 4 2 3 2 3 2A’ 1A’ 1 1
C(sp3)-H dehydrogenation Neutral Cation Y Y 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

14 TOF Mass Spectrum of Y + Isobutene Reaction

15 PIE Curve of m/z 143, Y(C4H6)

16 Experimental and Simulated Spectra
46309 / 45367 364 / 349 388 / 380 236 (?) Experimental 1A1  2A1 250 K 25 cm-1 FWHM 1A1  2A1 5 K 25 cm-1 FWHM

17 AIE and Vibrational Frequencies (cm-1)
Y(C4H6), C3v isomer MATI BPW91 AIE: 1A1 ¬ 2A1 46309 45367 Assignment 388 380 n 𝟔 +

18 Geometries (C3v) Neutral Cation 2A1 1A1 2.465 2.427 2.321 2.349 1.442
C(sp3)-H dehydrogenation Neutral Cation 2.465 2.427 2.321 2.349 1.442 1.439 CCC=115.10° CCC=114.68° 2A1 1A1 C-C : 1.54 C=C : 1.34 Unit: Å

19 Conclusions Both Y + 1-butene and Y + isobutene reactions produce Y(C4H6) by dehydrogenation from C(sp3)-H bonds. The complex from the Y + 1-butene reaction has a Cs structure, while that from isobutene reaction has a C3v structure. Compared to La + butene reactions, the Y reactions produce metal-hydrocarbon complexes with similar structures.

20 Thank you Any Questions?

21

22 Neutral Ion 2A' 4A" 1A' 3A" Point Group CS E0 (cm-1) 0.00 Y - C1 (Å) 2.39 2.66 2.33 2.57 Y - C2 (Å) 2.55 2.48 C1 - C2 (Å) 1.45 1.40 1.46 C2 - C3 (Å) Ð C1-C2-C3 124 123

23 Neutral Cation 1 4 1 4 2 3 2 3 2A’ 1A’ 4 4 1 1 2 3 2 3 4A’’ 3A’’

24 Vibrational Frequencies (ion only)
Y(C4H6), CS isomer MATI BPW91 AIE: 1A' ¬ 2A' 43473 43014 Assignment (Calc.) 10 0 1 798 794 11 0 1 502 524 12 0 1 422 422 13 0 1 350 328

25 Vibrational Frequencies (cm-1)
Y(C4H6), CS isomer MATI BPW91 AIE: 1A' ¬ 2A' 43473 43014 Assignment (Calc.) 10 0 1 798 794 11 0 1 502 524 11 1 0 -492 -498 12 0 1 422 422 12 1 0 -400 -387

26 Vibrational Frequencies
Y(C4H6), CS isomer MATI BPW91 AIE: 1A' ¬ 2A' 43473 43014 Assignment (Calc.) 13 0 1 350 328 13 1 0 -310 -280

27 MATI Spectrum of Y(C4H6)

28 Possible Structures? (C3V or C1?) Electronic States
Geometry optimization and frequency calculations were carried at BPW91/ G** for C, H and LANL2DZ for Yttrium Electronic States Relative Energies (cm-1) 2A1 (neutral) 4A (neutral) 17054 1A1 (ion) 45367 3A (ion) 56522 IE (cm-1) 1A1 ¬ 2A1 IE (cm-1) 3A ¬ 4A 39468 IE (exp) = cm-1 3A  2A cm-1 (high energy) : omitted

29 Wiley-McLaren Time-of-Flight Mass Spec.
Metal Atom reaction? Wiley-McLaren Time-of-Flight Mass Spec. MCP Detector 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

30 Metal Atom reaction?

31 Metal Atom reaction?

32 Metal Atom reaction?

33 Metal Atom reaction? (Pre-mixture gas)

34 Metal Atom reaction?

35 Metal Atom reaction?

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