A guided ion beam tandem mass spectrometer is used to examine the kinetic energy dependence of reactions of Pt+ with NO, NO2 and N2O, and PtO+ with NO and NO2, as well as collision-induced decomposition (CID) of PtO+ with N2 and PtNO+ with Xe. Pt+ reacts with NO and NO2 most efficiently by charge transfer, although oxygen atom transfer is also prominent for NO2 and the dominant reaction with N2O. Charge transfer is also the most efficient process observed for PtO+ + NO, whereas this ion reacts with NO2 by inefficient oxygen atom transfer, and in the reaction of PtO+ with N2, only simple CID and ligand exchange are observed. Analysis of the kinetic energy dependences for endothermic reaction cross sections yields the 0 K bond dissociation energies (BDEs) in eV (kJ mol−1) of D0(Pt+–N) = 3.35 ± 0.08 (323 ± 8), D0(Pt–N) = 3.84 ± 0.10 (371 ± 10), D0(Pt+–NO) = 3.13 ± 0.07 (302 ± 7) and D0(Pt+–O) = 3.26 ± 0.07 (315 ± 7). The bond energy of D0(Pt+–O) is consistent with our previous results and confirmed by results for nearly thermoneutral reactions here. Combining the BDEs of PtN+ and PtN measured here with literature data yields the ionization energy of PtN as 9.45 ± 0.13 eV.
SomorjaiG.A., Introduction to Surface Chemistry and Catalysis.Wiley, New York (1994).
2.
CrabtreeR.H., The Organometallic Chemistry of the Transition Metals, 2nd Edn.Wiley, New York (1994).
3.
TaylorK., in Catalysis (Science and Technology), Vol. 5, Ed by AndersonJ.R.BoudartM., Springer-Verlag, Berlin, p. 119 (1984).
4.
ArmentroutP.B.KickelB.L., in Organometallic Ion Chemistry, Ed by FreiserB.S., Kluwer, Dordrecht, p. 1 (1996).
5.
ArmentroutP.B., in Topics in Organometallic Chemistry, Vol. 4–I, Ed by BrownJ.M.HofmannP., Springer-Verlag, Berlin, p. 1 (1999).
6.
KretzschmarI.SchröderD.SchwarzH.ArmentroutP.B., in Adv. Met. & Semicon. Clusters, Vol. 5, Ed by DuncanM., Elsevier, New York, p. 347 (2001).
7.
ArmentroutP.B., “The Kinetic Energy Dependence of Ion-Molecule Reactions: Guided Ion Beams and Threshold Measurements”, Int. J. Mass Spectrom.200, 219 (2000).
8.
ZhangX.-G.ArmentroutP.B., “Activation of O2, CO, and CO2 by Pt+: The Thermochemistry of PtO+”, J. Phys. Chem. A107, 8904 (2003).
9.
ZhangX.-G.ArmentroutP.B., “Activation of O2 and CO2 by PtO+: The Thermochemistry of PtO2+”, J. Phys. Chem. A107, 8915 (2003).
10.
BrönstrupM.SchröderD.KretzschmarI.SchwarzH.HarveyJ.N., “Platinum Dioxide Cation: Easy to Generate Experimentally but Difficult to Describe Theoretically”, J. Am. Chem. Soc.123, 142 (2001).
11.
AristovN.ArmentroutP.B., “Collision Induced Dissociation of Vanadium Monoxide Ion”, J. Phys. Chem.90, 5135 (1986).
12.
LohS.K.FisherE.R.LianL.SchultzR.H.ArmentroutP.B., “State Specific Reactions of Fe+(6D, 4F) with O2 and cyclo-C2H4O: D°0(Fe+-O) and Effects of Collisional Relaxation”, J. Phys. Chem.93, 3159 (1989).
13.
LohS.K.LianL.ArmentroutP.B., “Oxidation Reactions at Variably Sized Transition Metal Centers: Fen+ and Nbn+ + O2 (n = 1 – 3)”, J. Chem. Phys.91, 6148 (1989).
14.
FisherE.R.ElkindJ.L.ClemmerD.E.GeorgiadisR.LohS.K.AristovN.SunderlinL.S.ArmentroutP.B., “Reactions of Fourth Period Metal Ions (Ca+ - Zn+) with O2: Metal Oxide Ion Bond Energies”, J. Chem. Phys.93, 2676 (1990).
15.
ClemmerD.E.ElkindJ.L.AristovN.ArmentroutP.B., “Reaction of Sc+, Ti+, and V+ with CO. MC+ and MO+ Bond Energies”, J. Chem. Phys.95, 3387 (1991).
16.
ClemmerD.E.DalleskaN.F.ArmentroutP.B., “Reaction of Zn+ with NO2. The Gas Phase Thermochemistry of ZnO”, J. Chem. Phys.95, 7263 (1991).
17.
ClemmerD.E.DalleskaN.F.ArmentroutP.B., “Gas Phase Thermochemistry of the Group 3 Dioxides: ScO2, YO2 and LaO2”, Chem. Phys. Lett.190, 259 (1992).
18.
SieversM.R.ArmentroutP.B., “The Potential Energy Surface for Carbon-Dioxide Activation by V+: A Guided Ion Beam Study”, J. Chem. Phys.102, 754 (1995).
19.
ChenY.-M.ArmentroutP.B., “Kinetic Energy Dependence of the Reactions of Ru+, Rh+, Pd+, and Ag+ with O2”, J. Chem. Phys.103, 618 (1995).
20.
SieversM.R.ChenY.-M.ArmentroutP.B., “Metal Oxide and Carbide Thermochemistry of Y+, Zr+, Nb+, and Mo+”, J. Chem. Phys.105, 6322 (1996).
21.
SieversM.R.ArmentroutP.B., “Gas Phase Activation of Carbon Dioxide by Niobium and Niobium Monoxide Cations”, Int. J. Mass Spectrom.179–180, 103 (1998).
22.
SieversM.R.ArmentroutP.B., “Reactions of CO and CO2 with Gas Phase Mo+, MoO+, and MoO2+”, J. Phys. Chem. A102, 10754 (1998).
23.
RodgersM.T.WalkerB.ArmentroutP.B., “Reactions of Cu+(1S and 3D) with O2, CO, CO2, NO, N2O, and NO2 Studied by Guided Ion Beam Mass Spectrometry”, Int. J. Mass Spectrom.182–183, 99 (1999).
24.
SieversM.R.ArmentroutP.B., “Reactions of Y+, YO+ and YO2+ with CO and CO2”, Inorg. Chem.38, 397 (1999).
25.
SieversM.R.ArmentroutP.B., “Oxidation of CO and Reduction of CO2 by Gas Phase Zr+, ZrO+, and ZrO2+”, Int. J. Mass Spectrom.185–187, 117 (1999).
26.
WeberM.E.ElkindJ.L.ArmentroutP.B., “Kinetic Energy Dependence of Al+ + O2 → AlO+ + O”, J. Chem. Phys.84, 1521 (1986).
27.
ClemmerD.E.WeberM.E.ArmentroutP.B., “Reactions of Al+(1S) with NO2, N2O and CO2: Thermochemistry of AlO and AlO+”, J. Phys. Chem.96, 10888 (1992).
28.
DalleskaN.F.ArmentroutP.B., “Guided Ion Beam Studies of Reactions of Alkaline Earth Ions with O2”, Int. J. Mass Spectrom. Ion Processes134, 203 (1994).
29.
LohS.K.HalesD.A.LianL.ArmentroutP.B., “Collision Induced Dissociation of Fen+ (n = 2 – 10) with Xe: Ionic and Neutral Iron Cluster Binding Energies”, J. Chem. Phys.90, 5466 (1989).
30.
SchultzR.H.ArmentroutP.B., “Reactions of N4+ with Rare Gases from Thermal to 10 eV c.m.: Collision Induced Dissociation, Charge Transfer, and Ligand Exchange”, Int. J. Mass Spectrom. Ion Processes107, 29 (1991).
31.
ZhangX.-G.ArmentroutP.B., “Reactions of Pt+ with H2, D2, and HD: Effect of Lanthanide Contraction on Reactivity and Thermochemistry”, J. Chem. Phys.116, 5565 (2002).
32.
ZhangX.-G.LiyanageR.ArmentroutP.B., “The Potential Energy Surface for Activation of Methane by Pt+: A Detailed Guided-Ion Beam Study”, J. Am. Chem. Soc.123, 5563 (2001).
33.
ZhangX.-G.ArmentroutP.B., “Sequential Bond Energies of Pt(CO)x+ (x = 1–4) Determined by Collision Induced Dissociation”, Organometallics20, 4266 (2001).
34.
TeloyE.GerlichD., “Integral Cross Sections for Ion-Molecule Reactions. 1. The Guided Beam Technique”, Chem. Phys.4, 417 (1974).
35.
GerlichD., “Inhomogeneous rf Fields: A Versatile Tool for the Study of Processes with Slow Ions”, Adv. Chem. Phys.82, 1 (1992).
36.
ErvinK.M.ArmentroutP.B., “Translational energy dependence of Ar+ + XY → ArX+ + Y (XY = H2, D2, HD) from thermal to 30 eV cm”, J. Chem. Phys.83, 166 (1985).
37.
ChantryP.J., “Doppler Broadening in Beam Experiments”, J. Chem. Phys.55, 2746 (1971).
38.
ChesnavichW.J.BowersM.T., “Theory of Translationally Driven Reactions”, J. Phys. Chem.83, 900 (1979).
39.
ArmentroutP.B., in Advances in Gas Phase Ion Chemistry, Vol. 1, Ed by AdamsN.G.BabcockL.M., JAI Press, Greenwich, p. 83 (1992).
40.
MunteanF.ArmentroutP.B., “Guided Ion Beam Study of Collision-Induced Dissociation Dynamics: Integral and Differental Cross Sections”, J. Chem. Phys.115, 1213 (2001).
41.
ChaseM.W.Jr, J. Phys. Chem. Ref. Data Monograph 9, NIST-JANAF Thermochemical Tables, 4th edition (1998).
42.
HuberK.P.HerzbergG., Molecular Spectra and Molecular Structure, I V. Constants of Diatomic Molecules.Van Nostrand Reinhold, New York (1979).
43.
ShimanouchiT., Tables of Molecular Vibrational Frequencies, Consolidated Vol. I. NSRDS-NBS 39 (1972).
44.
CitraA.AndrewsL., “Reactions of Laser-Ablated Palladium and Platinum Atoms with Nitric Oxide: Infrared Spectra and Density Functional Calculations of MNO+,0,- and M(NO)2 in Solid Argon and Neon”, J. Phys. Chem. A104, 8160 (2000).
45.
BeckeA.D., “Density-functional thermochemistry. III. The role of exact exchange”, J. Chem. Phys.98, 5648 (1993).
46.
LeeC.YangW.ParrR. G., “Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density”, Phys. Rev. B37, 785 (1988).
47.
FrischM.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.ZakrzewskiV.G.MontgomeryJ.A.JrStratmannR.E.BurantJ.C.DapprichS.MillamJ.M.DanielsA.D.KudinK.N.StrainM.C.FarkasO.TomasiJ.BaroneV.CossiM.CammiR.MennucciB.PomelliC.AdamoC.CliffordS.OchterskiJ.PeterssonG.A.AyalaP.Y.CuiQ.MorokumaK.MalickD.K.RabuckA.D.RaghavachariK.ForesmanJ.B.CioslowskiJ.OrtizJ.V.BaboulA.G.StefanovB.B.LiuG.LiashenkoA.PiskorzP.KomaromiI.GompertsR.MartinR.L.FoxD.J.KeithT.Al-LahamM.A.PengC.Y.NanayakkaraA.GonzalezC.ChallacombeM.GillP.M.W.JohnsonB.ChenW.WongM.W.AndresJ.L.GonzalezC.Head-GordonM.ReplogleE.S.PopleJ.A., Gaussian 98, Revision A.11.Gaussian, Inc., Pittsburgh, PA, USA (1998).
48.
HayP.J.WadtW.R., “Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals”, J. Chem. Phys.82, 299 (1985).
49.
OhanessianG.BrusichM.J.GoddardW.A.III, “Theoretical Study of Transition-metal Hydrides. 5. HfH+ through HgH+, BaH+, and LaH+”, J. Am. Chem. Soc.112, 7179 (1990).
50.
MarijnissenA.MeulenJ.J.HackettP.A.SimardB., “First ionization potential of platinum by mass-selected double-resonance field-ionization spectroscopy”, Phys. Rev. A52, 2606 (1995).
51.
ForesmanJ.B.FrischA.E., Exploring Chemistry with Electronic Structure Methods.Gaussian, Inc., Pittsburgh, PA, USA (1996).
GioumousisG.StevensonD.P., “Reactions of Gaseous Molecule Ions with Gaseous Molecules. V. Theory”, J. Chem. Phys.29, 294 (1958).
54.
ArmentroutP.B.SimonsJ., “Understanding Heterolytic Bond Cleavage”, J. Am. Chem. Soc.114, 8627 (1992).
55.
ThompsonC.J.StringerK.L.McWilliamsM.MetzR.B., “Electronic spectroscopy of predissociative states of platinum oxide cation”, Chem. Phys. Lett.376, 588 (2003).
56.
HeinemannC.KochW.SchwarzH., “An approximate method for treating spin-orbit effects in platinum”, Chem. Phys. Lett.245, 509 (1995).
57.
CitraA.WangX.BareW.D.AndrewsL., “Reactions of Laser-Ablated Platinum with Nitrogen: Matrix Infrared Spectra of Platinum Nitride, Complexes, and Anions”, J. Phys. Chem. A105, 7799 (2001).
58.
LiangB.ZhouM.AndrewsL., “Reactions of Laser-Ablated Ni, Pd, and Pt Atoms with Carbon Monoxide: Matrix Infrared Spectra and Density Functional Calculations on M(CO)n (n = 1–4), M(CO)n− (n = 1–3), and M(CO)n+ (n = 1–2), (M = Ni, Pd, Pt)”, J. Phys. Chem. A104, 3905 (2000).
59.
TjeltaB.L.ArmentroutP.B., “Gas-Phase Metal Ion Ligation: Collision-Induced Dissociation of Fe(N2)x+ (x = 1 – 5) and Fe(CH2O)x+ (x = 1 – 4)”, J. Phys. Chem. A101, 2064 (1997).
60.
SiegbahnP.E.M., “A comparison of the bonding in the second-row transition-metal oxides and carbenes”, Chem. Phys. Lett.201, 15 (1993).
