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 Current
Complexes
S. E. Novick et al, TH13. Inorg. Chem. 52
(2013), 816.
H. M. Pickett et al, TH16.
re= 0.809 Å
G.S. Grubbs et al, FC02.
re= 0.875 Å
re= 0.820 Å
re= 0.794 Å
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, 105-117
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-PPd,e & ECP60MDFd 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
bEvans,
Nuclear Quadrupole Coupling
Constant for 197Au
Nuclear Quadrupole Coupling
Constant for 197Au
Complex
free
Ar
Kr
Predicted H2
For CuF
complexes
S. E. Novick
et al, TH13
eQq 197Au (MHz)
9.63312(13)
-259.8352(21)
-349.857(23)
-7.2
eQq 35Cl (MHz)
-61.99694(81)
-54.0502(31)
-52.012(21)
-40.6
De (kJ/mol)
0
46.9
71.3
164
Extrapolating Au eQq
Complex
free
Ar
Kr
Predicted H2
eQq 197Au (MHz)
9.63312(13)
-259.8352(21)
-349.857(23)
-7.2
eQq 35Cl (MHz)
-61.99694(81)
-54.0502(31)
-52.012(21)
-40.6
De (kJ/mol)
0
46.9
71.3
164
eQq 197Au (MHz)
-900
-700
R² = 0.9977
-500
-30
-300
Kr AuCl
-100
100
eQq 35Cl
(MHz)
-50
Ar AuCl
AuCl
-70
Extrapolating Au eQq
Complex
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
Au(I) is 5d10
Inorg. Chem. 52 (2013), 816.
S. E. Novick TH13.
Complex Creation by
Laser Ablation
Albation plume in an Cl2,
H2, and Ar expansion
S. E. Novick et al, TH13
G.S. Grubbs II et al, FC02
Photo courtesy of Duminda Ranasinghe
Flow Controller
Flow Controller
Flow Control
Gas A
To Chamber
Gas B
Pressure
Gas C
Pressure
Transducer
Mass
Flow
Controller
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
≈ 150-170 MHz splitting
p-H2
197Au35Cl
≈ 10 MHz splitting
197Au37Cl
monomer
p-H2 AuCl
6 atm
9% H2, <0.05% Cl2, & Ar
2000 averages
p-H2 AuCl
Spectroscopic Constants
Au35Cl
Au37Cl
3292.2251(3)a
3146.2444(2)
/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
26
20
Parameter
(B+C)/2
ΔJ
Nc
/MHz
o-H2 AuCl
6 atm
9% H2, <0.05% Cl2 & Ar
5000 averages
Complex Dissociation Energies
Complex
Normalized Dissociation
Dissociation
Energy/α
Metal Halide Complex Energy kJ/mol
(kJ/mol Å3)
Reference
CuF
Ar
44
27
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
α
is
the
polarizability
of
the
complex partner
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
(rare
gas, N2, H29, or CO) Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
AgF
Ar
14
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
Normalized
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
AgCl
Xe
39
Complex
Dissociation10
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Dissociation
Energy/α 25
AuF
Xe
101
Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008
3
Metal
Halide
Complex
Energy
kJ/mol
(kJ/mol
Å
)
AuCl
Xe
80
20
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
AuF
Xe
101
25
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
N2
139
63
CO
150
65
Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136
Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822
CO
150
65
CuF
H2
60.2
91
Pickett, H. M., TH16
CuF
H2
60.2
91 141
CuCl
93
Grubbs, G. S. II, FC02
CuCl
H2
93
141 108
AgCl
71
This work
AgCl
H2
71
108 249
AuCl
164
AuCl
H2
164
249
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 Energies
Complex
Dissociation
Dissociation
Energy/α
Energy kJ/mol (kJ/mol Å3) Reference
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
42
4
Metal
Halide
AuCl
Complex
Ar
AuCl
Kr
44
3
AuCl
AuCl
AuF
AuF
AuF
AgBr
AgCl
AgCl
AgCl
AgCl
AgF
AgF
AgF
CuF
CuF
CuF
CuF
CuF
CuF
CuCl
CuCl
CuCl
CuCl
Xe
H2
Ar
Kr
Xe
Kr
Ar
Kr
Xe
H2
Ar
Kr
Xe
Ar
Kr
Xe
N2
CO
H2
Ar
Kr
Xe
H2
80
164
55
58
101
17
16
15
39
3
37
5
3
4
1
1
1
1
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
This work
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 17000-17008
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Grubbs, G. S. II; et al, FC02
14
17
43
44
48
59
139
150
60.2
33
39
51
93
1
1
2
4
3
2
9
10
14
3
2
2
21
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Francis, S. G.; Matthews, S. L.; Poleshcuk, I. K.; Walker, N. R.; Legon, A. C. Angew. Chem., Int. Ed. 2006, 45, 6341
Bera, J. K.; Samuelson, A. G.,; Chandresekhar, J. Organometallics, 1998, 17, 4136
Frohman, D. J.; Grubbs, G. S. II; Xhenhong, Y.; Novick, S. E. Inorgan. Chem. 2013. 52, 816-822
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Lovallo, C. C.; Klobukowski, M. Chem. Phys. Lett.2003, 589, 593
Thomas, J. M.; Walker, N. R.; Cooke, S. A.; Gerry, M. C. L. J. Am. Chem. Soc.2004, 126, 1235-1246
Pickett, H. M.; et al, TH16