june 22, 2012 67 th symp. on molec. spectrosc. laboratory detection of clznch 3 (x 1 a 1 ): further...
TRANSCRIPT
June 22, 201267th Symp. on Molec. Spectrosc.
Laboratory Detection of ClZnCH3 (X1A1): Further Evidence for Zinc Insertion
Matthew P. Bucchinoand
Lucy M. ZiurysDepartment of Chemistry
Steward ObservatoryUniversity of Arizona
97th Canadian Chemistry Conference and Exhibition June 3, 2014 69th Symp. on Molec. Spectrosc. June 18, 2014
June 22, 201267th Symp. on Molec. Spectrosc.69th Symp. on Molec. Spectrosc. June 18, 2014
More Negishi!!!
June 22, 201267th Symp. on Molec. Spectrosc.
Previous Work: ClZnCH3
M + CH4 → CH3–M–H (M = Pd, Be, Mg, Ca, Zn, Cd)M + CH3Cl → CH3–M–Cl (M = Pd, Mg, Zn, Cd)
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Instrumentation-Phase-locked Gunn oscillators and Schottky diode multipliers (65-750 GHz)-Gaussian beam optics-Reaction chamber: double-pass stainless steel cell-InSb He-cooled bolometer-Phase sensitive detection (2f)
Broida Oven Direct Absorption Spectrometer
68th Symp. on Molec. Spectrosc. June 19, 2013 97th Canadian Chemistry Conference and Exhibition June 3, 2014 69th Symp. on Molec. Spectrosc. June 18, 2014
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ClZnCH3 Synthesis• ClZnCH3 Synthesis
– Broida-type Oven → Zn vapor– 20 - 30 mTorr CH3Cl from top
– 15 mTorr Ar from bottom/side– 0.050 A (300 V) DC discharge
• IZnCH3 Synthesis– Broida-type Oven → Zn vapor– 2 mTorr CH3I from top
– 15 mTorr Ar from bottom/side– 0.060 A (640 V) DC discharge
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ClZnCH3 Direct Absorption Spectrum
Frequency (MHz)
K Components
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The Search for 66Zn and 37Cl Isotopologues
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Table of FrequenciesClZnCH3 (v = 0) ClZnCH3(v = 1) ClZnCH3(v = 2)
J′ ← J″ K νobs νobs-calc νobs νobs-calc νobs νobs-calc
48 47 0 239640.124 0.001
48 47 1 239636.352 -0.019
48 47 2 239624.829 0.023
48 47 3 239605.867 0.004
48 47 4 239579.362 0.031
48 47 5 … …
48 47 6 … …
58 57 0 296434.905 0.003 296015.086 -0.023
58 57 1 296430.244 0.007 296010.371 -0.074
58 57 2 296416.224 -0.020 295996.608 0.156
58 57 3 296392.910 -0.012 295973.076 -0.053
58 57 4 296360.258 -0.013 295940.438 -0.039
58 57 5 296318.288 -0.004 295898.533 0.036
58 57 6 296266.998 0.014 … …
230 – 300 GHz10 transitions of ClZnCH3 (v = 0,1) 4 transitions of ClZnCH3 (v = 2)
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Spectroscopic Constants ClZnCH3 (v = 0) ClZnCH3 (v = 1) ClZnCH3 (v = 2)
B 2558.3902(20) 2554.7678(14) 2551.2831(17)
DJ 0.000043355(32) 0.0000433020(23) 0.000043476(36)
DJK 0.04090(12) 0.040645(10) 0.040289(14)
HJK 0.102(19)x10-6 0.64(17) x10-7 …
rms 0.026 0.092 0.231
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Preliminary ClZnCH3Structure
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2.108 Å
ClZnCH3
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ClZnCH3 Formation: Zinc Insertion
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ClZnCH3 Current Problem • “Searches for the 37Cl, 66Zn, 13C, and D substituted
isotopologues are currently in progress.”
• Expensive– CH3Cl (≥99.5%)
• 1.8 kg for $475.00
– CD3Cl (99.5%)• 1 L for $550.00
– 13CH3Cl (99%)• 1 L for $753.00
mm
FTMW
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Future Work• Finish isotopic substitutions for ClZnCH3
– Cl66ZnCH3
– ClZn13CH3
– ClZnCD3
– 37ClZnCH3
• ClMgCH3
J. Organomet. Chem., 2006, 691, 4341–4349
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Thanks to…
Prof. Lucy ZiurysZiurys Group
Dr. Gilles AdandeDeWayne Halfen,Jessica Edwards,
Jie Min, Julie Anderson, Debbie Schmidt
FundingNSFNASA
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ClZnCH3 Problem #3: CH3Cl
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The Activation Strain Model
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ClZnCH3 Problem #2: Contaminants
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