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Rotational Spectra of Adducts of Pyridine with Methane and Its Halides

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Presentation on theme: "Rotational Spectra of Adducts of Pyridine with Methane and Its Halides"— Presentation transcript:

1 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 Bologna, Italy 2Departamento de Química Física y Química Inorganica, Facultad de Ciencias, Universidad de Valladolid, E Valladolid, Spain 3Departamento de Quimica Fisica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco,E Bilbao, Spain. Columbus

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

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

4 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, 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

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

6 Ab initio calculation MP2/ 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

7 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.

8 Rotational spectra Spectroscopic constants of the two isotopologues of PYR-CH4 [14N]PYR-CH4 [15N]PYR-CH4 A/MHz (9) (6) B/MHz (6) (6) C/MHz (6) (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

9 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

10 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) (Maa) (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

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

12 Ab initio calculation MP2/ 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

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

14 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 (6) (1) (4) (5) C/MHz 275 (6) (1) (4) (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

15 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,

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

17 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

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