TY - JOUR
T1 - Distortion of ethyne on formation of a π complex with silver chloride
T2 - C 2H 2Ag-Cl characterised by rotational spectroscopy and ab initio calculations
AU - Stephens, Susanna L.
AU - Mizukami, Wataru
AU - Tew, David P.
AU - Walker, Nicholas R.
AU - Legon, Anthony C.
N1 - Funding Information:
The authors thank the Engineering and Physical Sciences Research Council (UK) for a postgraduate studentship awarded to S.L.S. and project funding (EP/G026424/1). N.R.W. and D.P.T. thank the Royal Society for University Research Fellowships. A.C.L. is pleased to acknowledge the Leverhulme Trust for the award of an Emeritus Fellowship and the University of Bristol for a Senior Research Fellowship. W.M acknowledges the award of a Marie Curie Fellowship (IIF-301616). The authors are grateful to Professor Christine Willis and Amersham International for the gift of isotopically enriched CH. 13 2 2
PY - 2012/11/7
Y1 - 2012/11/7
N2 - C 2H 2Ag-Cl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. Reaction of laser-ablated silver metal with CCl 4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues 12C 2H 2 107Ag 35Cl, 12C 2H 2 109Ag 35Cl, 12C 2H 2 107Ag 37Cl, 12C 2H 2 109Ag 37Cl, 13C 2H 2 107Ag 35Cl, and 13C 2H 2 109Ag 35Cl were analysed to yield rotational constants A 0, B 0, and C 0, centrifugal distortion constants Δ J, Δ JK, and δ J, and Cl nuclear quadrupole coupling constants χ aa(Cl) and χ bb(Cl) -χ cc(Cl). A less complete analysis was possible for 12C 2D 2 107Ag 35Cl and 12C 2D 2 109Ag 35Cl. Observed principal moments of inertia were interpreted in terms of a planar, T-shaped geometry of C 2v symmetry in which the AgCl molecule lies along a C 2 axis of ethyne and the Ag atom forms a bond to the midpoint () of the ethyne π bond. r 0 and rm(1) geometries and an almost complete r s-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the CC bond and movement of the two H atoms away from the CC internuclear line and the Ag atom. The rm(1) bond lengths and angles are as follows: r(Ag) 2.1800(3) Å, r(C-C) 1.2220(20) Å, r(Ag-Cl) 2.2658(3) Å and the angle H-C has the value 187.79(1)°. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12)cc-pVTZ yield a r e geometry in excellent agreement with the experimental rm(1)version, including the ethyne angular distortion.
AB - C 2H 2Ag-Cl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. Reaction of laser-ablated silver metal with CCl 4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues 12C 2H 2 107Ag 35Cl, 12C 2H 2 109Ag 35Cl, 12C 2H 2 107Ag 37Cl, 12C 2H 2 109Ag 37Cl, 13C 2H 2 107Ag 35Cl, and 13C 2H 2 109Ag 35Cl were analysed to yield rotational constants A 0, B 0, and C 0, centrifugal distortion constants Δ J, Δ JK, and δ J, and Cl nuclear quadrupole coupling constants χ aa(Cl) and χ bb(Cl) -χ cc(Cl). A less complete analysis was possible for 12C 2D 2 107Ag 35Cl and 12C 2D 2 109Ag 35Cl. Observed principal moments of inertia were interpreted in terms of a planar, T-shaped geometry of C 2v symmetry in which the AgCl molecule lies along a C 2 axis of ethyne and the Ag atom forms a bond to the midpoint () of the ethyne π bond. r 0 and rm(1) geometries and an almost complete r s-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the CC bond and movement of the two H atoms away from the CC internuclear line and the Ag atom. The rm(1) bond lengths and angles are as follows: r(Ag) 2.1800(3) Å, r(C-C) 1.2220(20) Å, r(Ag-Cl) 2.2658(3) Å and the angle H-C has the value 187.79(1)°. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12)cc-pVTZ yield a r e geometry in excellent agreement with the experimental rm(1)version, including the ethyne angular distortion.
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U2 - 10.1063/1.4761895
DO - 10.1063/1.4761895
M3 - Article
C2 - 23145726
AN - SCOPUS:84868713153
SN - 0021-9606
VL - 137
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 17
M1 - 174302
ER -