1. HYDROGEN INTERACTION WITH METAL HALIDES: THE NUCLEAR QUADRUPOLE COUPLING CONSTANT OF GOLD IN THE p-H 2 -AuCl COMPLEX AND TRENDS IN THE OTHER HYDROGEN-COINAGE METAL HALIDE INTERACTIONS Daniel A. Obenchain, G.S. Grubbs II, Herbert M. Pickett, and Stewart E. Novick, Department of Chemistry, Wesleyan University, 52 Lawn Ave., Middletown, CT 06459-0180.

2. Previous and Current Complexes r e = 0.794 Å r e = 0.809 Å r e = 0.820 Å r e = 0.875 Å S. E. Novick et al, TH13. Inorg. Chem. 52 (2013), 816. H. M. Pickett et al, TH16. G.S. Grubbs et al, FC02. This Talk, FC03.

3. AuCl Complexes ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz) D e of Complex (kJ/mol) Monomer AuCl a 9.63312(13)-61.99694(81)0 Ar AuCl b -259.8352(21)-54.0502(31)46.9 Kr AuCl b -349.857(23)-52.012(21)71.3 Predicted H 2 AuCl -7.2-40.6164 a Evans, C. J.; Gerry, M. C. L. J. Mol. Spectrosc. 2000, 203, 105-117 b Evans, C. J.; Lesari, A.; Gerry, M. C. L. J. Am. Chem. Soc. 2000, 122, 6100-6105 c MP2/aug-cc-pVQZ (aug-cc-pVQZ-PP AVQZ-PP d,e & ECP60MDF d for Au) d Figgen, D.; Rauhut, G.; Dolg, M.; Stoll, H. Chem. Phys. 2005, 311, 227 e Peterson, K. A.; Puzzarini, C. Theor. Chem. Acc. 2005, 114, 283

4. Nuclear Quadrupole Coupling Constant for 197 Au

5. ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz)D e (kJ/mol) free9.63312(13)-61.99694(81)0 Ar-259.8352(21)-54.0502(31)46.9 Kr-349.857(23)-52.012(21)71.3 Predicted H 2 -7.2-40.6164 Nuclear Quadrupole Coupling Constant for 197 Au S. E. Novick et al, TH13 For CuF complexes

6. Extrapolating Au eQq ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz)D e (kJ/mol) free9.63312(13)-61.99694(81)0 Ar-259.8352(21)-54.0502(31)46.9 Kr-349.857(23)-52.012(21)71.3 Predicted H 2 -7.2-40.6164

7. Extrapolating Au eQq ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz) free9.63312(13)-61.99694(81) Ar-259.8352(21)-54.0502(31) Kr-349.857(23)-52.012(21) Predicted H 2 -7.2-40.6 Extrapolated H 2 -743.3-40.6 Experimental H 2 -817.9983(4)-41.709

8. H 2 Interaction with Metal Halides Inorg. Chem. 52 (2013), 816. S. E. Novick TH13. Au(I) is 5d 10

9. Complex Creation by Laser Ablation Photo courtesy of Duminda Ranasinghe S. E. Novick et al, TH13 G.S. Grubbs II et al, FC02 Albation plume in an Cl 2, H 2, and Ar expansion

10. Flow Controller

11. Gas A Gas B Gas C To Chamber Pressure Flow Control Mass Flow Controller Pressure Transducer

12. Flow Controller Saved significant time and sample in optimizing the relative ratios and total pressure of the gases used in the experiment By optimizing, we typically have improved signal strength ≈10

13. AuCl Spectral Splittings 197 Au 37 Cl monomer ≈ 10 MHz splitting ≈ 150-170 MHz splitting p-H 2 197 Au 35 Cl

14. p-H 2 AuCl 6 atm 9% H 2, <0.05% Cl 2, & Ar 2000 averages

15. p-H 2 AuCl Spectroscopic Constants ParameterAu 35 ClAu 37 Cl (B+C)/2 /MHz3292.2251(3) a 3146.2444(2) Δ J /kHz1.00(2)0.87(2) eQq Au /MHz-817.9983(4)-818.015(3) eQq Cl /MHz-41.709(1)-32.86(1) C I (Au) /kHz1.4(4)1.4(3) rms b /kHz2.31.6 NcNc 2620

16. o-H 2 AuCl 6 atm 9% H 2, <0.05% Cl 2 & Ar 5000 averages

17. Complex Dissociation Energies Metal HalideComplex Complex Dissociation Energy kJ/mol Normalized Dissociation Energy/α (kJ/mol Å 3 )Reference CuFAr44 27 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuClAr33 20 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgFAr14 9 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgClAr16 10 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AuFAr55 34 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuClAr42 26 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuFKr48 19 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuClKr39 16 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AgFKr17 7 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgClKr15 6 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgBrKr17 7 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AuFKr58 23 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuClKr44 18 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuFXe59 15 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuClXe51 13 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgFXe43 11 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AgClXe39 10 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AuFXe101 25 Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008 AuClXe80 20 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFN2N2 139 63 Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341 CuFCO150 65 Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136 CuFH2H2 60.2 91 Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822 CuClH2H2 93 141 Pickett, H. M., TH16 AgClH2H2 71 108 Grubbs, G. S. II, FC02 AuClH2H2 164 249 This work Metal HalideComplex Complex Dissociation Energy kJ/mol Normalized Dissociation Energy/α (kJ/mol Å 3 ) AuFXe101 25 CuFN2N2 139 63 CuFCO150 65 CuFH2H2 60.2 91 CuClH2H2 93 141 AgClH2H2 71 108 AuClH2H2 164 249 α is the polarizability of the complex partner (rare gas, N 2, H 2, or CO)

18. Conclusions Two isotopologues of p-H 2 AuCl have been assigned – Large changes in Cl and Au nuclear quadrupole coupling constant The donor of a complex significantly changing the field gradient around formally nd 10 atom in MX

19. Conclusions We suggest a medium strength interaction is present between the H 2 and M in the H 2 MX complexes presented at this conference r e = 0.875 Å

20. Future Work Searches for additional isotopologues and ortho-H 2 AuCl Additional studies have been started – H 2 AuF – H 2 AgF – H 2 ZnS – H 2 ZnO Possible inclusion of the bromides into the series

21. Acknowledgements NSF CHE-1011214 for $$$ Pete Pringle, Steve Cooke, Bob Bohn and Zbigniew Kisiel for many useful discussions

24. Dissociation Energies Metal HalideComplex Complex Dissociation Energy kJ/mol Dissociation Energy/α (kJ/mol Å 3 )Reference AuClAr424 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuClKr443 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuClXe803 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AuClH2H2 16437 This work AuFAr555 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuFKr583 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AuFXe1014 Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008 AgBrKr171 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AgClAr161 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AgClKr151 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgClXe391 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AgClH2H2 Grubbs, G. S. II; et al, FC02 AgFAr141 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgFKr171 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 AgFXe432 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFAr444 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuFKr483 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFXe592 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFN2N2 1399 Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341 CuFCO15010 Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136 CuFH2H2 60.214 Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822 CuClAr333 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuClKr392 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuClXe512 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246 CuClH2H2 9321 Pickett, H. M.; et al, TH16