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

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

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.

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 e) 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) O+O+ O2+O2+ pseudo 1 st order kinetics Slope = - k z/v

OH - + CH 3 Cl  Cl - + CH 3 OH k = 1.5 x cm 3 molecule -1 s -1 !! [cf: 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, (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, (1981). Transition from the Gas Phase to Solution _____________________________________________________________ T = 298 K

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, (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, (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 cm 3 molecule -1 s  2 K K = 2.2 x 10 7,  G o = kcal mol -1

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, (1980). XH + + Y  YH + + X Proton-Transfer and Proton Affinities __________________________________________________________

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, (1986) Electron Impact M Sifting Ions: One Major Reactant Ion (no Electrons) C 4 H C 4 H 2  C 8 H 4 +  C 6 H C 2 H 2 C 6 H C 4 H 2  C 10 H 4 +

________________________________________________________________ Ionic Origins of Carbenes in Space. D.K. Bohme. Nature 319, (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 +

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) Tetracyanocyclooctatetraene (Tetracyanosemibullvalene) Circumstellar Envelopes Titan’s Atmosphere mCID Synthesis of Exotic Carbon Rings ______________________________________________________

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 _______________________________________________________

_______________________________________________________________________________ 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, (1994). Penning Ionization He ( 3 S 1, 1 S 1 ) + C 60  He( 1 S 0 ) + C e “Electron Transfer/ Electron Detachment” He + + C 60  C He + e “Double-Electron Transfer/ Electron Detachment” Ar 2+ + C 60  C Ar + e Chemical Ionization of Fullerenes _____________________________________________

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

______________________________________________________________________ C 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, (1993).

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

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

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, (2000). Argon Plasma 5500 K P = 1 atm Aqueous solution of the atomic salt is injected via a nebulizer into the Ar plasma

Periodic Table of Atomic Salt Solutions

Primary Oxidation and Nitration Nb + + N 2 O  NbO + + N 2  NbN + + NO Further Oxidation NbO + + N 2 O  NbO N 2 NbN + + N 2 O  NbNO + + N 2 Clustering with N 2 O NbO 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.

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

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

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

61 atomic cations x 15 molecules = 915 reactions !! Web data base

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

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

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

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

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

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.

Ca ++ + O 3  CaO + + O 2 + (k = 1.5 × cm 3 mol -1 s -1 ) CaO + + O 3  CaO O 2 (k = 5 × cm 3 mol -1 s -1 ) CaO O 3  CaO O 2 (k = 6 × 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.

…..to DNA _______________________________________________________________________________ Protonation and Hydrobromination of (AGTCTG-5H)  M in 20/80 CH 3 OH/H 2 O + HBr k obs k obs /k c x10 -9 cm 3 s -1

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