HYDROGEN INTERACTION WITH METAL HALIDES: THE NUCLEAR QUADRUPOLE COUPLING CONSTANT OF GOLD IN THE p-H2-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.

Previous and CurrentComplexes

re= 0.794 Å

re= 0.809 Å

re= 0.820 Å

re= 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.

AuCl Complexes

Complex eQq 197Au (MHz) eQq 35Cl (MHz)De of

Complex (kJ/mol)

Monomer AuCla 9.63312(13) -61.99694(81) 0

Ar AuClb -259.8352(21) -54.0502(31) 46.9

Kr AuClb -349.857(23) -52.012(21) 71.3

Predicted H2 AuCl -7.2 -40.6 164

a Evans, C. J.; Gerry, M. C. L. J. Mol. Spectrosc. 2000, 203, 105-117bEvans, C. J.; Lesari, A.; Gerry, M. C. L. J. Am. Chem. Soc. 2000, 122, 6100-6105c MP2/aug-cc-pVQZ (aug-cc-pVQZ-PP AVQZ-PPd,e & ECP60MDFd for Au)d Figgen, D.; Rauhut, G.; Dolg, M.; Stoll, H. Chem. Phys. 2005, 311, 227e Peterson, K. A.; Puzzarini, C. Theor. Chem. Acc. 2005, 114, 283

Nuclear Quadrupole Coupling Constant for 197Au

Complex eQq 197Au (MHz) eQq 35Cl (MHz) De (kJ/mol)free 9.63312(13) -61.99694(81) 0Ar -259.8352(21) -54.0502(31) 46.9Kr -349.857(23) -52.012(21) 71.3

Predicted H2 -7.2 -40.6 164

Nuclear Quadrupole Coupling Constant for 197Au

S. E. Novick et al, TH13

For CuF complexes

Extrapolating Au eQqComplex eQq 197Au (MHz) eQq 35Cl (MHz) De (kJ/mol)

free 9.63312(13) -61.99694(81) 0Ar -259.8352(21) -54.0502(31) 46.9Kr -349.857(23) -52.012(21) 71.3

Predicted H2 -7.2 -40.6 164

Extrapolating Au eQqComplex eQq 197Au (MHz) eQq 35Cl (MHz)

free 9.63312(13) -61.99694(81)

Ar -259.8352(21) -54.0502(31)

Kr -349.857(23) -52.012(21)

Predicted H2 -7.2 -40.6

Extrapolated H2 -743.3 -40.6

Experimental H2 -817.9983(4) -41.709

H2 Interaction with Metal Halides

Inorg. Chem. 52 (2013), 816.S. E. Novick TH13.

Au(I) is 5d10

Complex Creation by Laser Ablation

Photo courtesy of Duminda Ranasinghe

S. E. Novick et al, TH13G.S. Grubbs II et al, FC02

Albation plume in an Cl2, H2, and Ar expansion

Flow Controller

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

197Au37Cl monomer

≈ 10 MHz splitting≈ 150-170 MHz splitting

p-H2 197Au35Cl

p-H2 AuCl

6 atm 9% H2, <0.05% Cl2, & Ar2000 averages

p-H2 AuClSpectroscopic Constants

Parameter Au35Cl Au37Cl

(B+C)/2 /MHz 3292.2251(3)a 3146.2444(2)

ΔJ /kHz 1.00(2) 0.87(2)

eQq Au /MHz -817.9983(4) -818.015(3)

eQq Cl /MHz -41.709(1) -32.86(1)

CI (Au) /kHz 1.4(4) 1.4(3)

rmsb /kHz 2.3 1.6

Nc 26 20

o-H2 AuCl6 atm9% H2, <0.05% Cl2 & Ar5000 averages

Complex Dissociation EnergiesMetal Halide Complex

Complex Dissociation

Energy kJ/mol

Normalized Dissociation Energy/α

(kJ/mol Å3) ReferenceCuF Ar 44 27 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuCl Ar 33 20 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgF Ar 14 9 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgCl Ar 16 10 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AuF Ar 55 34 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuCl Ar 42 26 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuF Kr 48 19 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuCl Kr 39 16 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AgF Kr 17 7 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgCl Kr 15 6 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgBr Kr 17 7 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AuF Kr 58 23 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuCl Kr 44 18 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuF Xe 59 15 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuCl Xe 51 13 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgF Xe 43 11 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AgCl Xe 39 10 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AuF Xe 101 25 Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008

AuCl Xe 80 20 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuF N2 139 63 Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341

CuF CO 150 65 Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136

CuF H2 60.2 91Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822

CuCl H2 93 141Pickett, H. M., TH16

AgCl H2 71 108Grubbs, G. S. II, FC02

AuCl H2 164 249This work

Metal Halide Complex

Complex Dissociation

Energy kJ/mol

Normalized Dissociation

Energy/α(kJ/mol Å3)

AuF Xe 101 25CuF N2 139 63CuF CO 150 65CuF H2 60.2 91CuCl H2 93 141AgCl H2 71 108AuCl H2 164 249

α is the polarizability of the complex partner (rare gas, N2, H2, or CO)

Conclusions

• Two isotopologues of p-H2 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 nd10 atom in MX

Conclusions

• We suggest a medium strength interaction is present between the H2 and M in the H2 MX complexes presented at this conference

re= 0.875 Å

Future Work• Searches for additional isotopologues and

ortho-H2 AuCl • Additional studies have been started– H2 AuF– H2 AgF– H2 ZnS– H2 ZnO

• Possible inclusion of the bromides into the series

Acknowledgements• NSF CHE-1011214 for $$$• Pete Pringle, Steve Cooke, Bob Bohn and

Zbigniew Kisiel for many useful discussions

Dissociation EnergiesMetal Halide Complex

Complex Dissociation

Energy kJ/mol

Dissociation Energy/α

(kJ/mol Å3) ReferenceAuCl Ar 42 4 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuCl Kr 44 3 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuCl Xe 80 3 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AuCl H2 164 37 This work

AuF Ar 55 5 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuF Kr 58 3 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AuF Xe 101 4 Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008

AgBr Kr 17 1 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AgCl Ar 16 1 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AgCl Kr 15 1 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgCl Xe 39 1 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

AgCl H2Grubbs, G. S. II; et al, FC02

AgF Ar 14 1 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgF Kr 17 1 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

AgF Xe 43 2 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuF Ar 44 4 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuF Kr 48 3 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuF Xe 59 2 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuF N2 139 9 Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341

CuF CO 150 10 Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136

CuF H2 60.2 14 Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822

CuCl Ar 33 3 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuCl Kr 39 2 Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593

CuCl Xe 51 2 Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246

CuCl H2 93 21 Pickett, H. M.; et al, TH16