Halogen bonding vs hydrogen bonding: CHF2INH3 vs CHF2IN(CH3)3

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Presentation transcript:

Halogen bonding vs hydrogen bonding: CHF2INH3 vs CHF2IN(CH3)3 Chris Medcraft Dror Bittner, Nick Walker Yannick Geboes, Wouter Herrebout

Introduction CHF2I can form halogen or hydrogen bonds When is halogen bonding energetically favoured over hydrogen bonding?

Halogen bond Electrostatic potential of Br2 Halogen bond describes attractive interaction between electron donor (e.g. NH3) and a halogen atom. + A.C. Legon, PCCP, 2010, 12, 7736 S.L. Stephens et al., PCCP, 2011, 13, 20736

Chirped-pulse Fourier transform microwave spectrometer (CP-FTMW) Nd:Yag 532 nm laser ~25 mJ/pulse N. R. Walker et al., Phys. Chem. Chem. Phys., 16, 2014, 25221

Halogen vs Hydrogen bond Halogen bond predicted to be more stable for trimethylamine a a ΔE = 0 kJ/mol ΔE = 2.7 kJ/mol Halogen bonded Hydrogen bonded A [MHz] 3182.9 1432.3 B [MHz] 494.0 540.7 C [MHz] 477.1 462.2 μA/μB/μC [D] 2.4/0.0/1.2 2.9/1.0/0.0 MP2/aug-cc-pvdz

CHF2I---N(CH3)3 50 261K FIDs Intensity [μV] 7 8 9 10 11 18 12 13 14 15 261K FIDs Intensity [μV] 7 8 9 10 11 18 12 13 14 15 16 17 Frequency [GHz]

CF2HI---N(CH3)3 3 261K FIDs Intensity [μV] 7 8 9 10 11 18 12 13 14 15 7 8 9 10 11 18 12 13 14 15 16 17 Frequency [GHz]

J = 14  13 J = 15  14 2 2.5 Intensity [μV] Intensity [μV] Ka=1 Ka=1 Ka=1 Ka=1 13.7 13.8 13.9 14.7 14.8 14.9 Frequency [GHz] Frequency [GHz] Halogen bonded Hydrogen bonded ‘Fit’ A [MHz] 3182.9 1432.3 ?? B [MHz] 494.0 540.7 501.2 C [MHz] 477.1 462.2 484.4 μA/μB/μC [D] 2.4/0.0/1.2 2.9/1.0/0.0 a-type

Iodine Nuclear Quadrupole Coupling Constants χaa(I) CF3I monomer -2145.017(11) CHF2I monomer -1817.9143(34) -NH3 -2230.124(75) -N(CH3)3 -2241.61(17) -2071(15) -84Kr −2125.09(63) -CO -2144.832(45) -H2S -2166.55(11) -H2O -2199.275(84) -N2 −2135.71(13) a a MP2/aug-cc-pvdz+ANO-RCC CF3I---N(CH3)3 CHF2I---N(CH3)3 Halogen bond Hydrogen bond χaa -2241.62(47) -2071(15) -2669.0 -190.4 χbb-cc 18(62) 91.9 -2566.3

I C O H3N I H2O I I H2S I C2H4 1 S.L. Stephens et al., Phys. Chem. Chem. Phys. 13 20736 (2011) 2 S.L. Stephens et al., J. Chem. Phys. 135 224309 (2011)

CF3I14NH3 Free rotation of NH3 Energy/MHz 13850 13855 13860 13865 13870 13875 A species sim. E species sim. Total (A and E) sim. CF3I14NH3 Frequency [MHz] S.L. Stephens et al., PCCP, 2011, 13, 20736

Large amplitude motion(s)

CHF2I---NH3 127K b a a a ΔE=2.5 kJ/mol MP2/aug-cc-pvdz ΔE = 0 kJ/mol Frequency [MHz] Halogen bonded Hydrogen bonded A [MHz] 8765.9 2155.3 B [MHz] 1034.5 1462.1 C [MHz] 960.5 1041.3 μA/μB/μC [D] 2.7/0.0/1.0 2.1/2.9/0.0

CF3I---CO2 J = 19  18 J = 11  10 1.1M FIDs Frequency [MHz] 8120 8140 14020 14030 14040 Frequency [MHz] Frequency [MHz]

CF3I---CO2 Structural Analysis 12C16O2----ICF3 13C16O2----ICF3 12C18O2----ICF3 B [MHz] 369.44584(14) 364.53189(16) 349.46529(17) DJ [kHz] 0.16799(20) 0.16398(23) 0.15831(25) DJK [kHz] 134.994(81) 131.40(14) 131.26(12) Χaa(I) [MHz] -2129.02(60) -2130.81(85) -2128.22(91) Number 392 290 195 σRMS [kHz] 31.0 29.9 24.9 r0 = 3.1977(2) Å

Outlook Throw data away and cry in the corner New spectrometer Tektronix SX 100GS/s Scope (32+Hz) 2-8 GHz TWT 2-18 GHz Horns Measure lower J’s Easier to analyse?

Acknowledgements Newcastle University Nick Walker John Mullaney Dror Bittner Argonne National Laboratory Daniel Zaleski University of Bristol Tony Legon Colin Western

BICF3 Complexes I C O H3N I H2O I H2S I C2H4 1 S.L. Stephens et al., Phys. Chem. Chem. Phys. 13 20736 (2011) 2 S.L. Stephens et al., J. Chem. Phys. 135 224309 (2011)

BCF3I vs BICl k(BICl) k(BICF3) NH3 H2S H2O N2 CO Kr Complexes formed between B and ICl are more strongly bound than those formed between B and ICF3. Both series provide evidence for formation of halogen bonds.