1. June 22, 2012 67 th Symp. on Molec. Spectrosc. Laboratory Detection of ClZnCH 3 (X 1 A 1 ): Further Evidence for Zinc Insertion Matthew P. Bucchino and Lucy M. Ziurys Department of Chemistry Steward Observatory University of Arizona 97 th Canadian Chemistry Conference and Exhibition June 3, 2014 69 th Symp. on Molec. Spectrosc. June 18, 2014

2. June 22, 2012 67 th Symp. on Molec. Spectrosc. 69 th Symp. on Molec. Spectrosc. June 18, 2014 More Negishi!!!

3. June 22, 2012 67 th Symp. on Molec. Spectrosc. Previous Work: ClZnCH 3 M + CH 4 → CH 3 –M–H (M = Pd, Be, Mg, Ca, Zn, Cd) M + CH 3 Cl → CH 3 –M–Cl (M = Pd, Mg, Zn, Cd) 69 th Symp. on Molec. Spectrosc. June 18, 2014

4. June 22, 2012 67 th Symp. on Molec. Spectrosc. 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 68 th Symp. on Molec. Spectrosc. June 19, 2013 97 th Canadian Chemistry Conference and Exhibition June 3, 2014 69 th Symp. on Molec. Spectrosc. June 18, 2014

5. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Synthesis –Broida-type Oven → Zn vapor –20 - 30 mTorr CH 3 Cl from top –15 mTorr Ar from bottom/side –0.050 A (300 V) DC discharge IZnCH 3 Synthesis –Broida-type Oven → Zn vapor –2 mTorr CH 3 I from top –15 mTorr Ar from bottom/side –0.060 A (640 V) DC discharge 69 th Symp. on Molec. Spectrosc. June 18, 2014

6. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Direct Absorption Spectrum Frequency (MHz) K Components 69 th Symp. on Molec. Spectrosc. June 18, 2014

7. June 22, 2012 67 th Symp. on Molec. Spectrosc. The Search for 66 Zn and 37 Cl Isotopologues 69 th Symp. on Molec. Spectrosc. June 18, 2014

8. June 22, 2012 67 th Symp. on Molec. Spectrosc. Table of Frequencies ClZnCH 3 (v = 0)ClZnCH 3 (v = 1)ClZnCH 3 (v = 2) J′←J″Kν obs ν obs-calc ν obs ν obs-calc ν obs ν obs-calc 48 470239640.1240.001 48 471239636.352-0.019 48 472239624.8290.023 48 473239605.8670.004 48 474239579.3620.031 48 475…… 48 476…… 58 570296434.9050.003296015.086-0.023 58 571296430.2440.007 296010.371 -0.074 58 572296416.224-0.020295996.608 0.156 58 573296392.910-0.012295973.076 -0.053 58 574296360.258-0.013295940.438 -0.039 58 575296318.288-0.004295898.533 0.036 58 576296266.9980.014 … … 230 – 300 GHz 10 transitions of ClZnCH 3 (v = 0,1) 4 transitions of ClZnCH 3 (v = 2) 69 th Symp. on Molec. Spectrosc. June 18, 2014

9. June 22, 2012 67 th Symp. on Molec. Spectrosc. Spectroscopic Constants ClZnCH 3 (v = 0)ClZnCH 3 (v = 1)ClZnCH 3 (v = 2) B2558.3902(20)2554.7678(14)2551.2831(17) DJDJ 0.000043355(32)0.0000433020(23)0.000043476(36) D JK 0.04090(12)0.040645(10)0.040289(14) H JK 0.102(19)x10 -6 0.64(17) x10 -7 … rms0.0260.0920.231 69 th Symp. on Molec. Spectrosc. June 18, 2014

10. June 22, 2012 67 th Symp. on Molec. Spectrosc. Preliminary ClZnCH 3 Structure 69 th Symp. on Molec. Spectrosc. June 18, 2014 2.108 Å ClZnCH 3

11. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Formation: Zinc Insertion 69 th Symp. on Molec. Spectrosc. June 18, 2014

12. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Current Problem “Searches for the 37 Cl, 66 Zn, 13 C, and D substituted isotopologues are currently in progress.” Expensive –CH 3 Cl (≥99.5%) 1.8 kg for $475.00 –CD 3 Cl (99.5%) 1 L for $550.00 – 13 CH 3 Cl (99%) 1 L for $753.00 mm FTMW 69 th Symp. on Molec. Spectrosc. June 18, 2014

13. June 22, 2012 67 th Symp. on Molec. Spectrosc. Future Work Finish isotopic substitutions for ClZnCH 3 –Cl 66 ZnCH 3 –ClZn 13 CH 3 –ClZnCD 3 – 37 ClZnCH 3 ClMgCH 3 J. Organomet. Chem., 2006, 691, 4341–4349 69 th Symp. on Molec. Spectrosc. June 18, 2014

14. June 22, 2012 67 th Symp. on Molec. Spectrosc. Thanks to…  Prof. Lucy Ziurys  Ziurys Group  Dr. Gilles Adande  DeWayne Halfen,Jessica Edwards, Jie Min, Julie Anderson, Debbie Schmidt  Funding  NSF  NASA 68 th Symp. on Molec. Spectrosc. June 19, 2013 69 th Symp. on Molec. Spectrosc. June 18, 2014

15. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Problem #3: CH 3 Cl 69 th Symp. on Molec. Spectrosc. June 18, 2014

16. June 22, 2012 67 th Symp. on Molec. Spectrosc. The Activation Strain Model 69 th Symp. on Molec. Spectrosc. June 18, 2014

17. June 22, 2012 67 th Symp. on Molec. Spectrosc. ClZnCH 3 Problem #2: Contaminants 69 th Symp. on Molec. Spectrosc. June 18, 2014

18. June 22, 2012 67 th Symp. on Molec. Spectrosc. 69 th Symp. on Molec. Spectrosc. June 18, 2014