Microwave Spectra and Structures of H 2 S-CuCl and H 2 S-AgCl Nicholas R. Walker, David Wheatley, Anthony C. Legon 64 th OSU International Symposium on Molecular Spectroscopy by 1 25 th June, 2009.

Introduction Bonding between sulfur and copper is recurring motif of inorganic chemistry. Explore and extend the range of L- MX species that can be generated using a laser ablation source. Ziurys and co-workers studied CuSH and many other metal hydrosulfides. [Janczyk, A.; Walter, S.K.; Ziurys, L.M.; Chem. Phys. Lett (2005)] Previous studies by laser ablation have explored OC-MX, Ar-MX, Kr-MX, Xe-MX; (Gerry and co-workers), N 2 -CuF (Bristol). Provides opportunity to compare molecular geometry of H 2 S-MCl with H 2 S-HCl, H 2 S-ICl, H 2 S-BrCl studied by Legon and co-workers.

Ar/H 2 S/CCl 4

Pump Nozzle and Cu rod Lens 532 nm Ar/H 2 S/CCl 4 supersonic expansion

End view S H H Å 92.1˚ Side view ClMS H θ r MCl r MS Structure of H 2 S-MCl  HSH and r SH bond distances assumed to be equal to free H 2 S. Experiment aims to determine r MCl, r MS, and angle between axes of MCl and H 2 S units.

F 1 -F 1 , F-F  = J-J  = 3-2

H 2 S- 63 Cu 35 ClH 2 S- 65 Cu 35 Cl / MHz (36) (49) D J  10 3 / MHz (95)0.2436(15) / MHz (20) (28) / MHz (31)57.230(7)  10 3 / MHz 5.654(82)5.26(15) H 2 S- 63 Cu 37 ClH 2 S- 65 Cu 37 Cl / MHz (12) (52) D J  10 3 / MHz (40)0.226(12) / MHz (7) (25) / MHz61.832(12)57.40(11)  10 3 / MHz 5.16(24)5.45(31)

r CuCl r CuS θ / ˚ r 0 structure2.0631(3)2.1532(3) (16) Frequency / MHz F 1 -F 1 , F-F  =, 6-5, 7-6, 4-3 D 2 S-Cu 35 Cl 63 Cu 65 Cu J-J  = gas pulses

Frequency / MHz H 2 S- 107/109 Ag 37 Cl 1700 gas pulses = F-F  J-J  = 4-3

H 2 S- A Ag 37 ClH 2 S- B Ag 37 Cl / MHz (18) (35) D J  10 3 / MHz (31)0.1827(96) / MHz (49) (66) H 2 S- A Ag 35 ClH 2 S- B Ag 35 Cl / MHz (67) (12) D J  10 3 / MHz (13)0.1758(24) / MHz (20) (35) r AgCl r AgS θ / ˚ r 0 structure (9) (9) (5)

H 2 S-MCl a MCl r MCl / År MS / Åθ / ˚r e / Å H 2 S-CuCl b c H 2 S-AgCl b H 2 S-HCl d [1.274] e CuSH (r m (1)) f (  Cu-S-H) a.All H 2 S-MCl structures are r 0. b.This work. c.Manson, E.L.; De Lucia, F. C.; Gordy, W.; J. Chem. Phys., (1975). d.Goodwin, E.J.; Legon, A.C.; J. Chem. Soc. Faraday Trans. 2: Molecular and Chemical Physics, 80(1) (1984). e.Fixed to r e value for HCl. f.Janczyk, A.; Walter, S.K.; Ziurys, L.M.; Chem. Phys. Lett (2005)

[ ( 63 Cu)] / MHz [ ( 35 Cl)] / MHz CuCl Ar-CuCl Kr-CuCl H 2 S-CuCl OC-CuCl Comparison of Nuclear Quadrupole Coupling Constants a.C.J. Evans and M.C.L. Gerry, J. Chem. Phys. 112, 1321 (2000) b.J.M. Michaud, S.A. Cooke and M.C.L. Gerry, Inorg. Chem. 43, 3871, (2004) c.N.R. Walker and M.C.L. Gerry, Inorg. Chem. 40, 6158 (2001) (a) (b) (c)

Acknowledgements The Royal Society Engineering and Physical Sciences Research Council (U.K.) H 2 S-MCl generated and studied in the gas phase for the first time where M=Cu or Ag. MCl distance only slightly longer than in free MCl in both cases. Angle between axes of H 2 S and MCl units measured. Angle is larger than in H 2 S-HCl in both cases. MS distances in both H 2 S-CuCl and H 2 S-AgCl are significantly shorter than in H 2 S-HCl. Conclusions Vacancies (available to EU or UK residents) EPSRC-funded PhD studentship available. 1 year postdoctoral assistantship available.