1. Gaseous Ions and Chemical Mass Spectrometry Diethard K. Böhme Ion Chemistry Laboratory Department of Chemistry Centre for Research in Mass Spectrometry Centre for Research in Earth & Space Science York University, Toronto, Canada CIC Medal Lecture Winnipeg, 2007

2. Gaseous Ions _____________________________________________________ C +, Fe +, Si +, Mg + H 3 + CH 5 + N 2 H + O 2 +, N 2 + HCO + H 3 O +, HCNH + HC 3 NH + NH 2 OH + + H 3 NCH 2 CH 2 COOH O 2 - OH -, CH3O - H 3 O + OH - (H 2 O) n CH3O - (CH 3 OH) n H 3 O + (H 2 O) n C 2 +, C 3 +, CN + C 3 H 3 +, SiC 10 H 8 + FeC 6 H 6 + _________________________________________________________________ “Ions are jolly little buggars, you can almost see them“ Ernest Rutherford Sr(C 60 ) 4 + C +, Fe +, Si +, Mg + H 3 +, CH 5 +, N 2 H +, HCO + HCNH +, HC 3 NH +, SiC 4 H +, SiC 10 H 8 + CH 3 +, C 2 H 2 +, C 2 H 3 +, C 3 H +, C 3 H 3 +, C 4 H 3 + C 3 N +, HCN +, HC 3 N +, C 60 +, C 60 ++, C 60 X + NH 2 OH +, + H 3 NCH 2 CH 2 COOH O -, O 2 -, OH -, OH - (H 2 O) n H 3 O +, H 3 O + (H 2 O) n CH 3 CNH + Ionospheric, Cometary and Interstellar Ions Ions Found in Solution 2+ OH -, CH 3 O -, C 2 H 5 O -, (CH 3 ) 3 CO - C 6 H 5 -, C 6 H 5 CH 2 -, C 6 H 5 C(CH 3 ) 2 -, t-BuC 6 H 5 -, H 3 O + (H 2 O) n, OH - (H 2 O) n, CH 3 O - (CH 3 OH) n, C 2 H 5 O - (C 2 H 5 OH) n, Ca 2+, Sr 2+, Ba 2+, H 3 O + C +, C 2 +, C 3 +, C 6 H 6 +, C 60 n+, C 70 n+ Fe + benzene, Fe + coronene Si + benzene, Si + naphthalene Carbonaceous Ions Atomic Cations Fe + Mg + Pt + La + Si + K+K+ Ca + Sc + Ti + Ar + V+V+ Cr + Mn + Co + Ni + Cu + Zn + Ga + Ge + As + Se + Rb + Sr + Y+Y+ Zr + Nb + Mo + Ru + Rh + Pd + Ag + Cd + In + Sn + Sb + Te + Cs + Ba + Hf + Ta + W+W+ Re + Os + Ir + Au + Hg + Tl + Pb + Bi + Ce + Pr + Nd + Sm + Eu + Gd + Tb + Dy + Ho + Er + Tm + Yb + Lu + Biological Ions (AGTCTG-5H + ) 5- Fe 3+ siderophore bleomycin + Zn 2+ penicillin

3. Looking for Ions in a Flowing Nitrogen Discharge Plasma ______________________________________________________ First quadrupole mass spectra (in Canada) _____________________________________________________ Mass Spectrometric Sampling Probe for Discharge Plasmas D.K. Böhme, J.M. Goodings. Rev. Sci. Instr. 37 (1966) 362. Ion Sampling Considerations for a Discharge Plasma of Nitrogen D.K. Böhme, J.M. Goodings. J. Appl. Phys. 37 (1966) 4261.

4. Ion Chemistry in a Flowing Helium Plasma ______________________________________________________ k A + + B  products - d[A + ]/dt = k [A + ][B] -v d[A + ]/dz = k [A + ][B] [A + ] z = [A + ] z=0 exp(-k[B]z/v) t = z/v [B] >> [A + ] In He at 0.35 Torr, 296 K (O 2 + e  O +, O 2 + + 2e) O + + H 2  OH + + H OH + + H 2  H 2 O + + H H 2 O + + H 2  H 3 O + + H _______________________________________________________________________________________________________________________________________________ Fehsenfeld, F. C.; Schmeltekopf, A. L.; Ferguson, E. E. “Thermal-energy ion-neutral reaction rates. VII. Some hydrogen-atom abstraction reactions.” J. Chem. Phys. 46 (1967) 2802-8. O+O+ O2+O2+ pseudo 1 st order kinetics Slope = - k z/v

6. OH - + CH 3 Cl  Cl - + CH 3 OH k = 1.5 x 10 -9 cm 3 molecule -1 s -1 !! [cf: 10 -26 in H 2 O] __________________________________________________________________________________________ Gas-phase reactions of anions with halogenated methanes at 297 ± 2K. K. Tanaka, G.I. Mackay, J.D. Payzant, D.K. Bohme. Can. J. Chem. 54, 1643-59 (1976). Bridging the gap between the gas phase and solution: transition in the kinetics of nucleophilic displacement reactions. D.K. Bohme, G.I. Mackay. J. Am. Chem. Soc. 103, 978-9 (1981). Transition from the Gas Phase to Solution _____________________________________________________________ T = 298 K

7. Transition from the Gas Phase to Solution (cont’d) _____________________________________________________ _______________________________________________________________ Standard acidity scale. The pKa of alcohols in the gas phase. D.K. Bohme, E. Lee-Ruff, L.B. Young. J. Am. Chem. Soc. 93, 4608-9 (1971). Acidity order of selected Broensted acids in the gas phase of 300K. D.K. Bohme, E. Lee-Ruff, L.B. Young. J. Am. Chem. Soc. 94, 5153-9 (1972). Bridging the gap between the gas phase and solution: transition in the relative acidity of water and methanol at 296 ± 2 K. G.I. Mackay, D.K. Bohme. J. Am. Chem. Soc. 100, 327 (1978). OH - + CH 3 OH  CH 3 O - + H 2 O, k = 1.5 x 10 -9 cm 3 molecule -1 s -1 296  2 K K = 2.2 x 10 7,  G o = - 9.9 kcal mol -1

8. X - + YH  Y - + XH XH + + Y  YH + + X ________________________________________________________________________________________ Determination of proton affinities from the kinetics of proton transfer reactions. VII. The proton affinities of O 2, H 2, Kr, O, N 2, Xe, CO 2, CH 4, N 2 O, and CO. D.K. Bohme, G.I. Mackay, H.I. Schiff. J. Chem. Phys. 73, 4976-86 (1980). XH + + Y  YH + + X Proton-Transfer and Proton Affinities __________________________________________________________

9. Selected-Ion Flow Tube (SIFT) Tandem Mass Spectrometry ______________________________________________________ ____________________________________________________________________________________________ Studies of reactions involving C 2 H x + ions with hydrogen cyanide using a modified selected ion flow tube. G.I. Mackay, G.D. Vlachos, D.K. Bohme, H.I. Schiff. Int. J. Mass Spectrom. & Ion Physics, 36, 259 (1980). Ion-molecule reactions with carbon chain molecules: reactions with diacetylene and the diacetylene cation. S. Dheandhanoo, L. Forte, A. Fox, D.K. Bohme. Can. J. Chem. 64, 641-8 (1986) Electron Impact M Sifting Ions: One Major Reactant Ion (no Electrons) C 4 H 2 + + C 4 H 2  C 8 H 4 +  C 6 H 2 + + C 2 H 2 C 6 H 2 + + C 4 H 2  C 10 H 4 +

10. ________________________________________________________________ Ionic Origins of Carbenes in Space. D.K. Bohme. Nature 319, 473-4 (1986) Ionic Origins of Carbenes in Space ______________________________________________________ Carbenes occur widely in the Universe :CH 2, :C=C:, :C=S, :C=O, :C =NH, :C=C=C:, l,c-:C 3 H 2, :C 3 O Their origin may involve ionizing radiation. Only H 2 C 4 : has not yet been observed in space. e + propylene  C 3 H +

11. Mg(HC 3 N) n-1 +  + HC 3 N  Mg(HC 3 N) n +  + h, n  0 Mg(HC 3 N) n +  + e  (HC 3 N) n + Mg _______________________________________________________________ Extraordinary Cluster Formation and Intramolecular Ligand-Ligand Interactions in Cyanoactylene Mediated by Mg +· : Implications for the Atmospheric Chemistry of Titan and for Circumstellar Chemistry. Rebecca Milburn, Alan C. Hopkinson, Diethard K. Bohme, J. Am. Chem. Soc. 127 (2005)13070-78. Tetracyanocyclooctatetraene (Tetracyanosemibullvalene) Circumstellar Envelopes Titan’s Atmosphere mCID Synthesis of Exotic Carbon Rings ______________________________________________________

12. NH 3(s) + H 2 O (s) NH 2 OH h h NO + 3H h, heat NH 2 OH Interstellar ice Interstellar gas h /A + RH + NH 2 OH 2 + NH 2 OH + CH 3 COOH CH 3 CH 2 COOH CH 3 COOH CH 3 CH 2 COOH NH 2 CH 2 COOH + NH 2 CH 2 CH 2 COOH + NH 3 CH 2 COOH + NH 3 CH 2 CH 2 COOH + -H 2 O M M+M+ NH 2 CH 2 COOH NH 2 CH 2 CH 2 COOH e-e- H _______________________________________________________________________________ Gas-phase syntheses for interstellar carboxylic and amino acids. Blagojevic et al., Mon. Not. R. Astron. Soc. 339 (2003) L7-L11. Ions and Life _______________________________________________________

13. _______________________________________________________________________________ Fullerene Cation and Dication Production by Novel Thermal-Energy Reactions of He +, Ne +, and Ar + with C 60. G. Javahery, S. Petrie, J. Wang and D.K. Bohme. Chem. Phys. Lett., 195, 7-10 (1992). Electron-Transfer Reactions with Buckminsterfullerene, C 60, in the Gas Phase. D.K. Bohme, Int. Reviews in Physical Chemistry, 13, 163-185 (1994). Penning Ionization He ( 3 S 1, 1 S 1 ) + C 60  He( 1 S 0 ) + C 60 + + e “Electron Transfer/ Electron Detachment” He + + C 60  C 60 2+ + He + e “Double-Electron Transfer/ Electron Detachment” Ar 2+ + C 60  C 603+ + Ar + e Chemical Ionization of Fullerenes _____________________________________________

14. Playing Chemistry with Buckyballs ____________________________________________________ C 60 + C 60 2+ _____________________________________________________________________________________________________ Derivatization of the Fullerene Dications C 60 2+ and C 70 2+ by Ion-Molecule Reactions in the Gas Phase. S. Petrie, G. Javahery, J. Wang and D.K. Bohme. J. Am. Chem. Soc., 114, 9177-9181 (1992). Gas-Phase Reactions of the Buckminsterfullerene Cations C 60.+, C 60 2+ and C 60.3+ with Water, Alcohols and Ethers. R. Javahery, S. Petrie, H. Wincel, J. Wang and D.K. Bohme. J. Am. Chem. Soc., 115, 6295-6301 (1993).

15. ______________________________________________________________________ C 60 3+ Charge ………! ___________________________________________________________ Gas-Phase Reactions of Fullerene Monocations, Dications and Trications with Nitriles. G. Javahery, S. Petrie, J. Wang, H. Wincel and D.K. Bohme. J. Am. Chem. Soc., 115, 9701-9707 (1993).

16. _______________________________________________________________________ Fullerene Ions in the Gas Phase: Chemistry as a Function of Charge State. D.K. Bohme, Can. J. Chem. 77, 1453-1464 (1999). Chemistry is increasingly pre-empted by physics (e transfer) with increasing charge state. Chemistry as a Function of Charge State _________________________________________________________________

18. Gas-Phase Surface Chemistry ____________________________________________________ _____________________________________________________________________________________________________________________ The Influence of Surface Strain on the Chemical Reactivity of Fullerene Ions: Addition Reactions with Cyclopentadiene and 1,3-Hexadiene.. Becker, L.T. Scott and D.K. Bohme, Int. J. Mass Spectrom. Ion Processes 167/168, 519 (1997). Enhanced Reactivity of Fullerene Cations Possessing Adjacent Pentagons. S. Petrie and D.K. Bohme. Nature, 365, 426. (1993). (C surface) + + c-C 5 H 6  addition The Influence of Curvature (Strain) Metal-Cation Ligation on Curved Carbonaceous Surfaces

19. The ICP/SIFT/QqQ instrument _____________________________________________________ __________________________________________________________________________________________________________ An Inductively-Coupled Plasma / Selected-Ion Flow Tube Mass Spectrometer Study of the Chemical Resolution of Isobaric Interferences. G.K. Koyanagi, V.I. Baranov, S. Tanner and D.K. Bohme, J. Anal. At. Spectr. 15, 1207-1210 (2000). Argon Plasma 5500 K P = 1 atm Aqueous solution of the atomic salt is injected via a nebulizer into the Ar plasma

20. Periodic Table of Atomic Salt Solutions

21. Primary Oxidation and Nitration Nb + + N 2 O  NbO + + N 2  NbN + + NO Further Oxidation NbO + + N 2 O  NbO 2 + + N 2 NbN + + N 2 O  NbNO + + N 2 Clustering with N 2 O NbO 2 + + N 2 O  NbO 2 (N 2 O) + NbO 2 (N 2 O) + +N 2 O  NbO 2 (N 2 O) 2 + NbO 2 (N 2 O) 2 + +N 2 O  NbO 2 (N 2 O) 3 + NbNO + + N 2 O  NbNO(N 2 O) + NbNO(N 2 O) + +N 2 O  NbNO(N 2 O) 2 + NbNO(N 2 O) 2 + +N 2 O  NbNO(N 2 O) 3 + Reactions of atomic cations: Nb + with N 2 O ______________________________________________________ ________________________________________________________________ V.V. Lavrov et al., J. Phys. Chem. A 106 (2002) 4581.

22. Surfing the Periodic Table with N 2 O ______________________________________________________ ________________________________________________________________ V.V. Lavrov et al., J. Phys. Chem. A 106 (2002) 4581. M + + N 2 O  MO + + N 2  MN + + NO  M + (N 2 O)

23. _____________________________________________________ G.K. Koyanagi, D.K. Bohme. J. Phys. Chem. A 105, 8964 (2001). Ln + + N 2 O  LnO + + N 2 Barriers to Electron Promotion ____________________________________________________

24. Arrhenius would be interested! ____________________________________________________ k exp = k c e -PE/RT

25. 61 atomic cations x 15 molecules = 915 reactions !! http://www.chem.yorku.ca/profs/bohme/research/research.html Web data base

26. The 87 Rb + (s 0 ) / 87 Sr + (s 1 ) Isobaric Interference Rb + (s 0 ) + SF 6  NR k  1x10 -13 cm 3 s -1 Sr + (s 1 ) + SF 6  SrF + + SF 5 97% k = 5.7x10 -10 cm 3 s -1  SrSF 5 + + F 3% Chemical Resolution in Elemental Analysis ____________________________________________________

27. C. Ping and D.K. Bohme, J. Phys.Chem. A, in preparation. Discontinuities in Reactivity: Opportunities for Chemical Resolution ____________________________________________________ M + + SF 6  MF n + + SF 6-n  M + (SF 6 )  SF n + + MF 6-n

28. Observed with: Fe +, Ge + Sr + Ba +, Os +, Ir + Eu +, Yb + ____________________________________________________ Blagojevic et al., Angew. Chem. Int. Ed. 2003, 42, 4923-4927 Atomic Ions: the Ultimate Sites for Catalysis _____________________________________________ Catalytic Reduction of N x O y by CO (O-atom Transport Mediated by M + )

29. __________________________________________________________________ V. Blagojevic, G. Orlova, D. K Bohme, J. Am. Chem. Soc. 127 (2005) 3545. GAUSSIAN98 B3LYP/sdd/6-311+G* Potential Energy Landscape for Catalysis ______________________________________________________

30. ICP/SIFT/QqQ mass spectrum Proposed tetrahedral structure for Sr(C 60 ) 4 + Packing Atomic Metal Cations with C 60 _____________________________________________________ _______________________________________________________________________ G.K. Koyanagi, J. Xu and D. K. Bohme, unpublished

31. The ESI/qQ/SIFT/QqQ instrument _____________________________________________________ A – skimmer, B – q0 reaction cell, C extended stubbies, D – extended q0 rod set _________________________________________________________________________________________ A novel chemical reactor suited for studies of biophysical chemistry: construction and evaluation of a selected ion flow tube utilizing an electrospray ion source and a triple quadrupole detection system. G.K. Koyanagi et al. Int. J. Mass Spectrom. In press, 2007.

32. Ca ++ + O 3  CaO + + O 2 + (k = 1.5 × 10 -9 cm 3 mol -1 s -1 ) CaO + + O 3  CaO 2 + + O 2 (k = 5 × 10 -10 cm 3 mol -1 s -1 ) CaO 2 + + O 3  CaO 3 + + O 2 (k = 6 × 10 -10 cm 3 mol -1 s -1 ) 100  M CaAcetate in H 2 O/CH 3 OH (1/1) From Atomic Dications…. _____________________________________________________ Oxidation of Ca ++ Initiated by Charge Separation.

33. …..to DNA _______________________________________________________________________________ Protonation and Hydrobromination of (AGTCTG-5H) 5- 50  M in 20/80 CH 3 OH/H 2 O + HBr k obs k obs /k c 3.2 0.68 2.6 0.78 1.9 0.77 1.3 0.80 x10 -9 cm 3 s -1

34. Greg Koyanagi Stefan Feil Janna Anichina Voislav Blagojevic Michael Jarvis Andrea Dasic Tuba Gozet Sara Hashemi Mike Duhig Svitlana Shcherbyna Acknowledgments