The rate and equilibrium kinetics of the reactions of the biologically important metal species M+, M+(pyrrole) and M+(pyrrole)2 (M = Ni, Cu) have been investigated with the biological gases CO2, D2O, NH3 and NO in the gas phase at 295 ± 2 K in helium buffer-gas at a pressure of 0.35 ± 0.01 Torr. The measurements were taken with an Inductively Coupled Plasma/Selected-Ion Flow Tube (ICP/SIFT) tandem mass spectrometer. Only ligation was observed for the reactions of bare Ni+ and Cu+ with CO2, D2O and NH3 with rates consistent with the known strengths of the resulting ligand–metal bonds. Both metal cations appeared to be oxidized and produce N2O in interesting reactions that are second order in NO. One pyrrole ligand was observed to increase the rate of ligation by as much as a factor of 100 and to switch off the oxidation with NO. Equilibrium was achieved for the ligation of CO2, D2O and NO to both Ni+(pyrrole) and Cu+(pyrrole), and so it was possible to determine absolute values for the standard free energies of ligation. No ligand substitution was observed with M+(pyrrole). M+(pyrrole)2 was observed to be generally unreactive towards the small molecules investigated: a notable exception is ammonia. Very fast ligand substitution reactions were observed for reactions of M+(pyrrole)2 with NH3.
PozharskiiA.F.SoldatenkovA.T.KatritzkyA.R., Heterocycles in Life and Society: An Introduction to Heterocyclic Chemistry and Biochemistry and the Role of Heterocycles in Science, Technology, Medecine and Agriculture.John Wiley & Sons, Chichester, UK (1997).
2.
TimmsP.L., “Transition metal vapors in chemical synthesis. Direct preparation of dibenzenechromium as an undergraduate experiment”, Chem. Educ.49, 782 (1972).
3.
SilverthornW.E., “Arene transition metal chemistry”, Adv. Organomet. Chem.13, 47 (1975).
FriendC.M.MuettertiesE.L., “Coordination chemistry of metal surfaces. 3. Benzene and toluene interactions with nickel surfaces”, J. Am. Chem. Soc.103, 773 (1981).
6.
LewisF.D.YangJ.SternC.L., “Ground and excited state aromatic-aromatic interactions with distance control by hydrogen bonding”, J. Am. Chem. Soc.118, 2772 (1996).
7.
MuehldorfA.V.EngenD.V.WarnerJ.C., “Aromatic-aromatic interactions in molecular recognition: A family of artificial receptors for thymine that shows both face-to-face and edge-to-face orientations”, J. Am. Chem. Soc.110, 6561 (1988).
8.
JorgensenW.L.SeveranceD.L., “Aromatic-aromatic interactions: Free energy profiles for the benzene dimer in water, chloroform, and liquid benzene”, J. Am. Chem. Soc.112, 4768 (1990).
9.
LaatikainenR.RatilainenJ.SebastianR.SantaH., “NMR study for benzene and some other fundamental aromatic systems using alignment of aromatics in strong magnetic field”, J. Am. Chem. Soc.117, 11006 (1995).
10.
KoyanagiG.K.BohmeD.K., “Kinetics and thermodynamics for the bonding of benzene to 20 main-group atomic cations: Formation of half-sandwiches, full-sandwiches and beyond”, Int. J. Mass Spectrom.227, 563 (2003).
11.
CaraimanD.KoyanagiG.K.BohmeD.K., “Gas-phase reactions of transition-metal ions with hexafluorobenzene: Room-temperature kinetics and periodicities in reactivity”, J. Phys. Chem. A108, 978 (2004).
12.
CaraimanD.BohmeD.K., “Periodic trends in reactions of benzene clusters of transition metal cations, M(C6H6)1,2+, with molecular oxygen”, J. Phys. Chem. A106, 9705 (2002).
13.
JarvisM.PisterziL.BlagojevicV.KoyanagiG.K.BohmeD.K., “Gas-phase kinetic measurements and quantum chemical calculations of the ligation of Ni+, Cu+, Ni+(pyrrole)1,2 and Cu+(pyrrole)1,2 with O2 and CO”, Int. J. Mass Spectrom.227, 161 (2003).
14.
NewkomeG.R.PaudlerW.W., Contemporary Heterocyclic Chemistry: Syntheses, Reactions, and Applications.Wiley, New York, USA (1982).
15.
HuangH.RodgersM.T., “Sigma versus pi interactions in alkali metal ion binding to azoles: Threshold collision-induced dissociation and ab initio theory studies”, J. Phys. Chem. A106, 4277 (2002).
16.
GapeevA.YangC.KlippensteinS.J.DunbarR.C., “Binding energies of gas-phase metal ions with pyrrole: Experimental and quantum chemical results”, J. Phys. Chem. A104, 3246 (2000).
17.
MuettertiesE.L.BleekeJ.R.WuchererE.J.AlbrightT.A., “Structural, stereochemical, and electronic features of arene-metal complexes”, Chem. Rev.82, 499 (1982).
18.
MeyerF.KhanF.A.ArmentroutP.B., “Thermochemistry of transition metal benzene complexes: Binding energies of M(C6H6)x+ (x = 1, 2) for M = Ti to Cu”, J. Am. Chem. Soc.117, 9740 (1995).
19.
RodgersM.T.ArmentroutP.B., “Noncovalent interactions of nucleic acid bases (uracil, thymine, and adenine) with alkali metal ions. Threshold collision-induced dissociation and theoretical studies”, J. Am. Chem. Soc.122, 8548 (2000).
20.
RodgersM.T.ArmentroutP.B., “Influence of d orbital occupation on the binding of metal ions to adenine”, J. Am. Chem. Soc.124, 2678 (2002).
21.
RodgersM.T.ArmentroutP.B., “Absolute alkali metal ion binding affinities of several azoles determined by threshold collision-induced dissociation”, Int. J. Mass Spectrom.185–187, 359 (1999).
22.
HuangH.RodgersM.T., “Sigma versus pi interactions in alkali metal ion binding to azoles: Threshold collision-induced dissociation and ab initio theory studies”, J. Phys. Chem. A106, 4277 (2002).
23.
AmunugamaR.RodgersM.T., “Absolute alkali metal ion binding affinities of several azines determined by threshold collision-induced dissociation and ab initio theory”, Int. J. Mass Spectrom.195–196, 439 (2000).
24.
StanleyJ.R.AmunugamaR.RodgersM.T., “Periodic trends in the binding of metal ions to pyridine studied by threshold collision-induced dissociation and density functional theory”, J. Am. Chem. Soc.122, 10969 (2000).
25.
RodgersM.T., “Substituent effects in the binding of alkali metal ions to pyridines, studied by threshold collision-induced dissociation and ab initio theory: The methylpyridines”, J. Phys. Chem A105, 2374 (2001).
26.
RodgersM.T., “Substituent effects in the binding of alkali metal ions to pyridines studied by threshold collision-induced dissociation and ab initio theory: The aminopyridines”, J. Phys. Chem A105, 8145 (2001).
27.
AmunugamaR.RodgersM.T., “Periodic trends in the binding of metal ions to pyrimidine studied by threshold collision-induced dissociation and density functional theory”, J. Phys. Chem A105, 9883 (2001).
28.
BakhtiarR.JacobsonD.B., “Transition-metal mediated heteroatom removal by reactions of FeL+ [L = O, C4H6, c-C5H6, c-C5H5, C6H6, C5H4(:CH2)] with furan, thiophene, and pyrrole in the gas phase”, J. Am. Soc. Mass Spectrom.7, 938 (1996).
29.
MackayG.I.VlachosG.D.BohmeD.K.SchiffH.I., “Studies of reactions involving C2Hx+ ions with hydrogen cyanide using a modified selected ion flow tube”, Int. J. Mass Spectrom. Ion Phys.36, 259 (1980).
30.
RaksitA.B.BohmeD.K., “Studies of reactions of C3H+ ions in the gas phase at 296 ± 2 K”, Int. J. Mass Spectrom. Ion Processes55, 69 (1983/84).
31.
KoyanagiG.K.LavrovV.BaranovV.I.BanduraD.TannerS.D.McLarenJ.W.BohmeD.K., “A novel inductively coupled plasma/selected-ion flow tube mass spectrometer for the study of reactions of atomic and atomic oxide ions”, Int. J. Mass Spectrom. Ion Processes194, L1 (2000).
32.
KoyanagiG.K.BaranovV.I.TannerS.D.BohmeD.K., “An inductively coupled plasma/selected-ion flow tube mass spectrometric study of the chemical resolution of isobaric interferences”, J. Anal. At. Spectrom.15, 1207 (2000).
33.
LavrovV.V.BlagojevicV.KoyanagiG.K.OrlovaG.BohmeD.K., “Gas-phase oxidation and nitration of first-, second, and third-row atomic cations in reactions with nitrous oxide: Periodicities in reactivity”, J. Phys. Chem. A108, 5610 (2004).
34.
SuT.ChesnavichJ., “Parametrization of the ion-polar molecule collision rate constant by trajectory calculations”, J. Chem. Phys.76, 5183 (1982).
35.
TonkynR.RonanM.WeisshaarJ.C., “Multicollision chemistry of gas-phase transition-metal ions with small alkanes: Rate constants and product branching at 0.75 Torr of helium”, J. Phys. Chem.92, 92 (1988).
36.
GoodA., “Classical semiempirical rate equation for third order ion-molecule association reactions”, Trans. Faraday Soc.67, 3495 (1971).
37.
LiasS.G.BartmessJ.E.LiebmanJ.F.HolmesJ.L.LevinR.D.MallardW.G., J. Phys. Chem. Ref. Data17, (Suppl. 1) (1988).
KoyanagiG.K.CaraimanD.BlagojevicV.BohmeD.K., “Gas-phase reactions of transition-metal ions with molecular oxygen: Room-temperature kinetics and periodicities in reactivity”, J. Phys. Chem. A106, 4581 (2002).
40.
RuschelG.K.NemetzT.M.BallD.W., “Matrix isolation and density functional studies of novel transition metal complexes. NO+Fe, Co, Ni, Cu, and Zn in argon matrixes”, J. Mol. Struct.384, 101 (1996).
41.
HollandP.M.CastlemanA.W., “Gas-phase complexes of copper(1+) and silver(1+) via thermionic emission sources”, J. Am. Chem. Soc.102, 6174 (1980).
42.
HollandP.M.CastlemanA.W., “The thermochemical properties of gas-phase transition metal ion complexes”, J. Chem. Phys.76, 4195 (1982).
43.
MagneraT.F.DavidD.E.StulikD.OrthR.G.JonkmanH.T.MichlJ., “Production of hydrated metal ions by fast ion or atom beam sputtering. Collision-induced dissociation and successive hydration energies of gaseous copper+ with 1–4 water molecules”, J. Am. Chem. Soc.111, 5036 (1989).
44.
MagneraT.F.DavidD.E.MichlJ., “Gas-phase water and hydroxyl binding energies for monopositive first-row transition metal ions”, J. Am. Chem. Soc.111, 4100 (1989).
45.
MarinelliP.J.SquiresR.R., “Sequential solvation of atomic transition-metal ions. The second solvent molecule can bind more strongly than the first”, J. Am. Chem. Soc.111, 4101 (1989).
46.
RosiM.BauschlicherC.W., “The binding energies of one and two water molecules to the first transition row metal positive ions”, J. Chem. Phys.90, 7264 (1989).
47.
BauschlicherC.W.LanghoffS.R.PartridgeH., “The binding energies of copper(1+)-water and copper(1+)-ammonia complexes (Cu+-(H2O)n and Cu+-(NH3)n (n = 1–4))”, J. Chem. Phys.94, 2068 (1991).
48.
DalleskaN.F.HonmaK.SunderlinL.S.ArmentroutP.B., “Solvation of transition metal ions by water. Sequential binding energies of M+(H2O)x (x = 1–4) for M = Ti to Cu determined by collision-induced dissociation”, J. Am. Chem. Soc.116, 3519 (1994).
49.
KhanF.A.SteeleD.L.ArmentroutP.B., “Ligand effects in organometallic thermochemistry: The sequential bond energies of Ni(CO)x+ and Ni(N2)x+ (x = 1–4) and Ni(NO)x+ (x = 1–3)”, J. Phys. Chem.99, 7819 (1995).
50.
MeyerF.ChenY.-M.ArmentroutP.B., “Sequential bond energies of Cu(CO)x+ and Ag(CO)x+ (x = 1–4)”, J. Am. Chem. Soc.117, 4071 (1995).
51.
GoebelS.HaynesC.L.KhanF.A.ArmentroutP.B., “Collision-induced dissociation studies of Co(CO)x+, x = 1–5: Sequential bond energies and the heat of formation of Co(CO)4”, J. Am. Chem. Soc.117, 6994 (1995).
52.
WalterD.ArmentroutP.B., “Sequential bond dissociation energies of M+(NH3)x (x = 1–4) for M = Ti-Cu”, J. Am. Chem. Soc.120, 3176 (1998).
53.
FosterM.S.BeauchampJ.L., “Gas-phase ion chemistry of iron pentacarbonyl by ion cyclotron resonance spectroscopy. New insights into the properties and reactions of transition metal complexes in the absence of complicating solvation phenomena”, J. Am. Chem. Soc.97, 4808 (1975).
54.
WeddleG.H.AllisonJ.RidgeD.P., “Competitive ligand substitution reactions in the gas phase: Ion-molecule reactions of ligand molecules with ions derived from nitrosyltricarbonylcobalt(0) and with lithium(1+) ion”, J. Am. Chem. Soc.99, 105 (1977).
55.
KoszinowskiK.SchröderD.SchwarzH.HolthausenM.C.SauerJ.KoizumiH.ArmentroutP.B., “Bond dissociation energies and structures of CuNO+ and Cu(NO)2+”, Inorg. Chem.41, 5882 (2002).
56.
ThomasJ.L.C.BauschlicherC.W.HallM.B., “Binding of nitric oxide to first-transition-row metal cations: An ab initio study”, J. Phys. Chem.101, 8530 (1997).
