Susanna L. Stephens, John Mullaney, Matt Sprawling Daniel P. Zaleski, Nick R. Walker, Antony C. Legon 69 th International Symposium on Molecular Spectroscopy,

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Presentation transcript:

Susanna L. Stephens, John Mullaney, Matt Sprawling Daniel P. Zaleski, Nick R. Walker, Antony C. Legon 69 th International Symposium on Molecular Spectroscopy, Champaign-Urbana, Illinois 20 th June 2014 Broadband rotational spectroscopy reveals structural distortion in ethene and ethyne on coordination to gold iodide

2008 Gold: Chemistry, Materials and Catalysis Theoretical chemistry of gold. III Pekka Pyykko, Chem. Soc. Rev., 2008, 37, 1967 M. Barysz and Y. Ishikawa (eds.), Relativistic Methods for Chemists, Challenges and Advances in Computational Chemistry and Physics 10, Springer Science+Business Media Theory and simulation in heterogeneous gold catalysis Coquet et al., Chem. Soc. Rev., 37, 2046 (2008)

C 2 H 4 ···AgCl JCP, 135, (2011)

Unbound AgI molecule Free I − ion Na +  I - χ(I) = MHz88% Cu-I χ(I) = MHz59% Ag-I χ(I) = MHz54% Au-I χ(I) = MHz26% H-I χ(I) = MHz21% The ionicity constant a measure of proton transfer -coupling of the spin of a quadrupolar nuclei with the overall rotation Ag χ aa (X) Nuclear quadrupole coupling constant in complex, eQq (n,1,0) (X) Nuclear quadrupole coupling constant that would result from a single electron in a np z orbital I ( MHz) C. H. Townes and B. P. Dailey, J. Chem. Phys., 17, 782 (1949)

Carbonyl metal halide series OC···MXMX χ aa (X)/MHzi C /%χ aa (X)/MHzi C /% CuCl CuBr CuI AgCl AgBr AgI AuCl AuBr AuI− − CO···AgI; JCP, 136, (2012)

Frequency /MHz ← J’ kakc F F ← J’’ kakc F F ← ← ← ← ← Spectrum of C 2 H 4 ···AuI

Frequency /MHz Spectrum of C 2 H 4 ···AuI

Frequency /MHz C 2 H 2 ···AuI C 2 D 2 ···AuI Spectrum of C 2 H 2 ···AuI ~ averages (<24 hrs) sample ~1 % CF 3 I, ~ 3 % C 2 H 4 balance 6 bar Ar

12 C 2 H 4 ···AuI 12 C 2 D 4 ···AuI 12 C 2 H 2 ···AuI 12 C 2 D 2 ···AuI A 0 /MHz 23805(13)16241(33)34409(41)25180(13) B 0 /MHz (60) (17) (13) (74) C 0 /MHz (63) (17) (12) (77)  JK /kHz (77)2.65(20)3.998(23)3.460(25)  J /Hz 29.08(18)23(6)31.69(23)30.25(26)  J /Hz 9.018(57)(9.018)8.5(24)(8.5) χ aa (Au) /MHz (63)-822.7(19) (57) (80) χ bb  χ cc (Au) /MHz (19)201.11(769)358.28(12)360.35(29) χ aa (I) /MHz (58)-972.1(12) (47) (83) χ bb  χ cc (I) /MHz (184) (83) (14) (28) N σ r.m.s. / kHz C 2 H 4 12 C 2 D 4 C 0 /MHz (1) 12 C 2 H 2 12 C 2 D 2 B 0 /MHz (54) C 2 H 4 ···AuI and C 2 H 2 ···AuI Spectral constants 12 C 2 H 4 J. Phys. Chem. A., 110, 7461 (2006), Mol. Phys., 104, 273 (2006), 12 C 2 D 4 Mol. Phys., 43, 737 (1981), 12 C 2 H 2 12 C 2 D 2 J. Phys. Chem. Ref. Data., 32, 921 (2003), OC···CuI Chem. Phys. Lett., 422, 192 (2006), OC···AuI Mol. Phys., 105, 861 (2007), C 2 H 4 ···CuI Unpublished work a a χ aa (Au)χ aa (I)χ aa (Cu)χ aa (I) AuI CuI OC···AuI OC···CuI C 2 H 4 ···AuI prediction from OC···MI C 2 H 4 ···CuI C 2 H 4 ···AuI prediction from MI

C 2 H 4 ···AuIC 2 H 2 ···AuI Experiment CCSD(T)-F12* aug-cc-pvtz (pp I and Ag) Experiment CCSD(T)-F12* aug-cc-pvtz (pp I and Ag) r 0 (Au-I) /Å (98) r 0 (*···AuI) /Å (18) r 0 (C-C) /Å(1.3796)1.3796(1.2342) r 0 (C-H) /Å(1.0827)1.0827(1.0685) r 0 (C-C-H) /°(7.30)7.30(13.85)13.85 Dipole μ A /Debey C2H4C2H4 C2H2C2H2 AuI r 0 (C-C) /Å1.3386(14) (6)r e (AuI) /Å (70) r 0 (C-H) /Å1.0849(13) (2) Experimental and ab initio geometries a

a C 2 H 4 ···AuIC 2 H 2 ···AuI Experiment CCSD(T)-F12* aug-cc-pvtz (pp I and Ag) Experiment CCSD(T)-F12* aug-cc-pvtz (pp I and Ag) A 0 /MHz34409(41) (41) B 0 /MHz (13) (13) C 0 /MHz (12) (12) Experimental and ab initio rotational constants 12 C 2 H 4 ···AuI 12 C 2 D 4 ···AuI 12 C 2 H 2 ···AuI 12 C 2 D 2 ···AuI k σ /Nm (2) 66.8(4) 54.8(4) 56.0(6) ω /cm (4)197(1) 192(2) P b /uA (1)17.89(1)14.80(2)20.23(2) P c /uA (2)3.345(2) (1)-0.187(2) Δ 0 /MHz0.2612(1)0.295(2)0.231(1)0.374(3) icic (5) (3)55.841(5) 12 C 2 H 4 P a /uA P b /uA D.J. Millen, Can. J. Chem., 63, 1477 (1985)

Acknowledgements Newcastle John Mullaney Matt Sprawling Nick Walker Daniel Zaleski Dror Bittner Tony Legon Bristol David Tew

r 0 (M-X)/År 0 (*···M)/Åi C /%ω /cm -1 k σ /Nm -1 AuI OC···AuI2.5336(4)2.501(1)57228(-) C 2 H 2 ···AuI2.475(40)2.20(20) (2)54.8(4) C 2 H 4 ···AuI (1)59.1(2) AgI (7)-54-- OC···AgI2.5336(4)2.051(1) C 2 H 2 ···AgI2.600(94)2.11(22)65161(2)35.5(1) C 2 H 4 ···AgI2.54(13)2.23(27)67166(1)41(1) CuI OC···CuI2.3563(4)1.8154(9)74-- C 2 H 2 ···CuI(2.220)(2.182)74-- C 2 H 4 ···CuI(2.356)(1.974)75-- AgCl C 2 H 2 ···AgCl2.2716(6)2.1841(82)74197(3)51.4(26) C 2 H 4 ···AgCl2.2724(8)2.2701(2)75202(3)57.2(21) C 2 H 4 ···AgCl JCP, 135, (2011); C 2 H 2 ···AgCl JCP, 137, (2012); AuI Gerry, JMSp 205, 344 (2001) OC···AuI Walker & Legon, Mol. Phys., 5, 861 (2007) OC···CuI Legon, Chem. Phys. Lett., 422, 192 (2006)