C-O and O-H Bond Activation of Methanol by Lanthanum Atom Ruchira Silva, Dilrukshi Hewage and...
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C-O and O-H Bond Activation of Methanol by Lanthanum Atom Ruchira Silva , Dilrukshi Hewage and Dong-Sheng Yang Department of Chemistry University of Kentucky Lexington, KY 40506-0055
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Transcript of C-O and O-H Bond Activation of Methanol by Lanthanum Atom Ruchira Silva, Dilrukshi Hewage and...
C-O and O-H Bond Activation of Methanol by Lanthanum Atom
Ruchira Silva, Dilrukshi Hewage and Dong-Sheng Yang
Department of ChemistryUniversity of Kentucky
Lexington, KY 40506-0055
Motivations and Background
C-O and O-H bond activation • Catalysts in cross coupling reactions
Decomposition of methanol• Alternative fuel
Reaction of M+ (M=Sc, Y, Lu) with methanol• M(OH) and M(OCH3) are the primary products
• Undergo subsequent reaction to produce M(OCH3)n [n=1-3]
• M. Azzaro, S. Breton, M. Decouzon, S. Geribaldi.; lnt. J. Mass Spectrom. Ion Processes 128, 1993, 1-20• Bradley, D.C.; Chem. Rev. 1989, 89, 1317-1322.• Kilbourn, B. T. Journal of the Less-Common Metals, 111, 1985, 1-8
Experimental Setup
Pulsed valve and La rod
Repeller and extraction cans
MCP
DP (2300 l/s)
HV
TOF
TP (400 l/s)
TP (4
00 l/
s)
1x10-6 torr2x10-4 torr
CH3OH
TOF of La with CH3OH
LaO
La(OH)(OCH3)
La(OH)2
LaO
La(OCH3)2
La(OH)(OCH3)
Increase in
CH3OH conc.
@ 41000 cm-1
40000 40500 41000 41500
Wavelength (cm-1)
MATI Spectrum of La(OH)2
663 663
* *110
0-0
127 127
• Andrews. L, Wang , X.;J. Phys. Chem. A 2006, 110, 4157-4168.
La-O stretching = 624 cm-1 La-O bending (Calc) = 112 cm-1
40000 40500 41000 41500
Wavelength (cm-1)
1A1 2A1, B3LYP @ 150 K
663/662
127/126 110/107
Measured and Simulated Spectra of La(OH)2
Expt. IP = 40145 ± 5 cm-1
Calc. IP= 40388 cm-1
0-0
38700 39000 39300 39600 39900
Wavelength (cm-1)
MATI Spectrum of La(OCH3)2
~ 440
52
PES of La(OCH3)2
Single isomer in ionic state [La, O, C, H]= 1280
La
O
CH
0 30 60 90 120 1500
1
2
3
12
34
Dihedral angle[La, O, C, H] (0)
Rela
tive
ener
gy (c
m-1
)
38700 39000 39300 39600 39900
Wavelength (cm-1)
1A 2A, B3LYP @ 150 K
Measured and Simulated Spectra of La(OCH3)2
Expt. IP = 38660 ± 5 cm-1
Calc. IP= 39040 cm-1
0-0
22229
464 1098
Conclusions
• O-H and C-O bond activation by neutral La atom
• Structures and electronic states of La(OH)2 and La(OCH3)2
• IPs & vibrational frequencies of La(OH)2 and La(OCH3)2
• CH3 torsion affects on the MATI spectrum
Thank you
