Rotational Spectra of Adducts of Pyridine with Methane and Its Halides

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Rotational Spectra of Adducts of Pyridine with Methane and Its Halides Qian Gou,1 Lorenzo Spada,1 Montserrat Vallejo-López,2  Alberto Lesarri,2 Emilio J. Cocinero,3 Walther Caminati1   1Dipartimento di Chimica “G. Ciamician” dell’Università, Via Selmi 2, I-40126 Bologna, Italy 2Departamento de Química Física y Química Inorganica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid, Spain 3Departamento de Quimica Fisica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco,E-48080 Bilbao, Spain. gouqian33@gmail.com 2014.06.19. Columbus

Pyridine (PYR) π – type complexes σ – type complexes π electronic system n-orbital σ – type complexes

π – type complexes PYR – He PYR – Ne PYR – Ar PYR – Kr PYR – Xe 3 J. Chem. Phys. 2007, 127, 034302 Chem. Commun. 1998, 2625. PYR – Ar PYR – Kr PYR – Xe Chem. Phys. Lett. 1996, 261, 267. J. Chem. Phys. 2007, 127, 034302. J. Chem. Phys. 2008, 129, 144301. 3

The H···N interaction is stronger than the H···F one! σ – type complexes Two CH-N weak hydrogen bond CH-F weak hydrogen bond N-F3 halogen bond PYR – CF4 PYR – CH2F2 J. Phys. Chem. A, 2013, 117, 11289. Chem. Phys. Lett. 2014, 591, 216. Free internal rotation of –CF3 Quite rigid CH-N weak hydrogen bond CH-F weak hydrogen bond CH-N weak hydrogen bond CH-F weak hydrogen bond PYR – CHF3 PYR – CH3F Chem. Eur. J. 2010, 16, 1761. Phys. Chem. Chem. Phys. 2014, 16, 2149. Internal rotation of –CF3 V3 = 1.55 kJ mol-1 The H···N interaction is stronger than the H···F one! Internal rotation of –CH3 V3 = 0.52 kJ mol-1

C-H···π Weak Hydrogen Bond PYR ─ CH4 Very weak C-H proton donor Phys. Chem. Chem. Phys. 2014, 16, 13041-13046.

Ab initio calculation MP2/6-311++G(d,p) calculated spectroscopic parameters of the plausible conformers of PYR-CH4   I II  A/B/C (MHz)  aa/ bb-cc (MHz) |a|/|b|/|c| (D) ∆E/∆EBSSE(cm-1) 2901/1895/1873 3.29/-6.28 0.4/2.3/0.0 0/0 5793/1128/950 -4.86/-1.95 2.7/0.2/0.0 346/19

Rotational spectra C-H···π interaction ″ Recorded 212←101 transition of the observed conformer of PYR–CH4 showing the 14N hyperfine structure. Each component line exhibits the instrumental Doppler doubling.

Rotational spectra Spectroscopic constants of the two isotopologues of PYR-CH4   [14N]PYR-CH4 [15N]PYR-CH4 A/MHz 2995.7148(9) 2961.1510(6) B/MHz 1873.3363(6) 1872.2691(6) C/MHz 1853.4941(6) 1838.9538(5) DJ/kHz 5.46(1) 5.33(2) DJK/kHz 53.70(6) [53.70] DK/kHz -56.59(8) [-56.59] d1/kHz -0.23(2) [-0.23] aa/MHz 3.251(5) - χbb-χcc/MHz -6.137(7) N 55 18 σ/kHz 2.6 2.2

Dissociation Energy ks = 16π4(μDRCM)2[4B4+4C4-(B-C)2(B+C)2]/(hDJ) Stretching force constant: ks = 16π4(μDRCM)2[4B4+4C4-(B-C)2(B+C)2]/(hDJ) 2.7 Nm-1 One-dimensional flexible model Lennard-Jones potential energy function for the dissociation of PYR-CH4. R. Meyer, J. Mol. Spectrosc. 1979, 76, 266

Two-Dimensional Flexible Model Internal Dynamics Two-Dimensional Flexible Model V(X, Y) = (1/2)[kxY2+ky(X-Xe)2] Maa = 1/2(-Ia+Ib+Ic), etc. Xe = 0.375(1) Å Z0 = 3.544(1) Å (a) Experimental and calculated data   Mgg(uÅ) ∆Mgg(uÅ) PYR PYR-CH4 Exptl. Calc. x 87.738(Maa) 85.794(Mbb) -1.944 y 83.974(Mbb) 82.906(Mcc) -1.068 -1.069 z 0(Mcc) 186.888(Maa) 186.888 186.842 (b) Determined parameters kx = ky = 21.34(1) cm-1 Xe = 0.375(1) Å Z0 = 3.544(1) Å R. Meyer, J. Mol. Spectrosc. 1979, 76, 266

Cl···N Halogen Bond PYR ─ CF3Cl “σ-hole”

Ab initio calculation MP2/6-311++G(d,p) shapes and spectroscopic parameters of the two most stable forms of PYR-CF3Cl. ∆E,∆E0,∆EBSSE/cm-1 0,0,0 27,45,47 ED(BSSE)/kJ·mol-1 10.2 4.5 A,B,C/MHz 2928,288,275 1935,410,409 χaa,χbb-χcc(N)/MHz -4.84,-1.84 3.44,-0.64 χaa,χbb-χcc (Cl)/MHz -75.10,-0.41 -72.18,-1.66 μa,μb,μc/D 4.0,0.0,0.0 0.93,2.39,0.0

Rotational spectra PYR(14N)-CF335Cl PYR(15N)-CF335Cl 131,12←121,11 F1′, F′←F1″, F″ PYR(14N)-CF335Cl PYR(15N)-CF335Cl

Rotational spectra Calculated and experimental rotational constants of CF3Cl-PYR   calc. 35Cl-14N 37Cl-14N 35Cl-15N 37Cl-15N A/MHz 2928 5883(1) 5866.8(6) 5896(4) 5879.1(6) B/MHz 288 295.5296(6) 295.1493(1) 294.9668(4) 294.58141(5) C/MHz 275 280.0613(6) 279.7193(1) 279.4986(4) 279.15084(5) χaa(N)/MHz -4.84 -4.95(7) [-4.95] - χbb-χcc(N)/MHz -1.84 -2.4(1) [-2.4] Χaa(Cl)/MHz -75.10 -75.5(5) -60.3(4) -76.9(3) -61.2 χbb-χcc(Cl)/MHz -0.41 -0.32

Internal Dynamics The effective rotational constants of the ground state (v = 0,  = 0) A00 = Ar + W00(2) Fa2 B00 = Br+ W00(2) Fb2 C00 = Cr+ W00(2) Fc2 V3 ≈ 7 cal mol-1 g = gI/Ig F = ħ/[2·(1-ggI/Ig)I] D. R. Herschbach, J. Chem. Phys. 1959, 31, 91-108.

Summary σ-type halogen bond complex Pseudo rare gas σ-type halogen bond complex Almost free internal rotation of –CF3

Thanks for attention! Acknowledgement Prof. W. Caminati Prof. S. Melandri Dr. L. B. Favero Dr. A. Maris Thanks for attention! Dr. L. Evangelisti Dr. F. Gang Dr. B.M. Giuliano Ms. C. Calabrese Mr. L. Spada Ms. M. Vallejo-López Ms. A. Vigorito