June 22, 2012 67 th Symp. on Molec. Spectrosc. Laboratory Detection of ClZnCH 3 (X 1 A 1 ): Further...

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!!!


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)

69th Symp. on Molec. Spectrosc. June 18, 2014


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


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



ClZnCH3 Direct Absorption Spectrum

Frequency (MHz)

K Components



The Search for 66Zn and 37Cl Isotopologues



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)



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



Preliminary ClZnCH3Structure


2.108 Å

ClZnCH3


ClZnCH3 Formation: Zinc Insertion



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



Future Work• Finish isotopic substitutions for ClZnCH3

– Cl66ZnCH3

– ClZn13CH3

– ClZnCD3

– 37ClZnCH3

• ClMgCH3

J. Organomet. Chem., 2006, 691, 4341–4349



Thanks to…

Prof. Lucy ZiurysZiurys Group

Dr. Gilles AdandeDeWayne Halfen,Jessica Edwards,

Jie Min, Julie Anderson, Debbie Schmidt

FundingNSFNASA

68th Symp. on Molec. Spectrosc. June 19, 2013 69th Symp. on Molec. Spectrosc. June 18, 2014

http://cos.arizona.edu/


ClZnCH3 Problem #3: CH3Cl



The Activation Strain Model



ClZnCH3 Problem #2: Contaminants


June 22, 201267th Symp. on Molec. Spectrosc.69th Symp. on Molec. Spectrosc. June 18, 2014

June 22, 2012 67 th Symp. on Molec. Spectrosc. Laboratory Detection of ClZnCH 3 (X 1 A 1 ): Further...

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