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

Previous and Current Complexes r e = Å r e = Å r e = Å r e = 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.

AuCl Complexes ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz) D e of Complex (kJ/mol) Monomer AuCl a (13) (81)0 Ar AuCl b (21) (31)46.9 Kr AuCl b (23) (21)71.3 Predicted H 2 AuCl a Evans, C. J.; Gerry, M. C. L. J. Mol. Spectrosc. 2000, 203, b Evans, C. J.; Lesari, A.; Gerry, M. C. L. J. Am. Chem. Soc. 2000, 122, 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

Nuclear Quadrupole Coupling Constant for 197 Au

ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz)D e (kJ/mol) free (13) (81)0 Ar (21) (31)46.9 Kr (23) (21)71.3 Predicted H Nuclear Quadrupole Coupling Constant for 197 Au S. E. Novick et al, TH13 For CuF complexes

Extrapolating Au eQq ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz)D e (kJ/mol) free (13) (81)0 Ar (21) (31)46.9 Kr (23) (21)71.3 Predicted H

Extrapolating Au eQq ComplexeQq 197 Au (MHz)eQq 35 Cl (MHz) free (13) (81) Ar (21) (31) Kr (23) (21) Predicted H Extrapolated H Experimental H (4)

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

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

Flow Controller

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

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

AuCl Spectral Splittings 197 Au 37 Cl monomer ≈ 10 MHz splitting ≈ MHz splitting p-H Au 35 Cl

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

p-H 2 AuCl Spectroscopic Constants ParameterAu 35 ClAu 37 Cl (B+C)/2 /MHz (3) a (2) Δ J /kHz1.00(2)0.87(2) eQq Au /MHz (4) (3) eQq Cl /MHz (1)-32.86(1) C I (Au) /kHz1.4(4)1.4(3) rms b /kHz NcNc 2620

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

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, CuClAr33 20 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, AgFAr14 9 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, AuClAr42 26 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, AgClKr15 6 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, AuClKr44 18 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, 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 AuFXe Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, AuClXe80 20 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFN2N Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341 CuFCO Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136 CuFH2H Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem , CuClH2H Pickett, H. M., TH16 AgClH2H Grubbs, G. S. II, FC02 AuClH2H This work Metal HalideComplex Complex Dissociation Energy kJ/mol Normalized Dissociation Energy/α (kJ/mol Å 3 ) AuFXe CuFN2N CuFCO CuFH2H CuClH2H AgClH2H AuClH2H α is the polarizability of the complex partner (rare gas, N 2, H 2, or CO)

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

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 = Å

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

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

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, AuClKr443 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, AuClXe803 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 AuClH2H This work AuFAr555 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, AuFKr583 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, AuFXe1014 Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, 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, AgFKr171 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, CuFKr483 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFXe592 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593 CuFN2N 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 CuFH2H Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem , CuClAr333 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 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, CuClH2H Pickett, H. M.; et al, TH16