![Page 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/1.jpg)
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.
![Page 2: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/2.jpg)
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.
![Page 3: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/3.jpg)
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
![Page 4: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/4.jpg)
Nuclear Quadrupole Coupling Constant for 197Au
![Page 5: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/5.jpg)
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
![Page 6: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/6.jpg)
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
![Page 7: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/7.jpg)
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
![Page 8: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/8.jpg)
H2 Interaction with Metal Halides
Inorg. Chem. 52 (2013), 816.S. E. Novick TH13.
Au(I) is 5d10
![Page 9: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/9.jpg)
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
![Page 10: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/10.jpg)
Flow Controller
![Page 11: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/11.jpg)
Flow Controller
Gas A
Gas B
Gas C
To Chamber
Pressure
Flow Control
Mass Flow Controller
Pressure Transducer
![Page 12: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/12.jpg)
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
![Page 13: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/13.jpg)
AuCl Spectral Splittings
197Au37Cl monomer
≈ 10 MHz splitting≈ 150-170 MHz splitting
p-H2 197Au35Cl
![Page 14: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/14.jpg)
p-H2 AuCl
6 atm 9% H2, <0.05% Cl2, & Ar2000 averages
![Page 15: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/15.jpg)
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
![Page 16: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/16.jpg)
o-H2 AuCl6 atm9% H2, <0.05% Cl2 & Ar5000 averages
![Page 17: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/17.jpg)
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)
![Page 18: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/18.jpg)
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
![Page 19: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/19.jpg)
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
![Page 20: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/20.jpg)
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
![Page 21: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/21.jpg)
Acknowledgements• NSF CHE-1011214 for $$$• Pete Pringle, Steve Cooke, Bob Bohn and
Zbigniew Kisiel for many useful discussions
![Page 22: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/22.jpg)
![Page 23: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/23.jpg)
![Page 24: 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](https://reader036.vdocument.in/reader036/viewer/2022081503/56649cec5503460f949b8235/html5/thumbnails/24.jpg)
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