Neutralization–reionization mass spectrometry is applied for the generation of low-valence iron derivatives. Neutralization of RFe+ (R = H, F, Cl, Br, I, CN, OH, NH2, acac, C6H5) ions resulted in the corresponding neutrals having lifetimes of at least 5 μs. Atom connectivities in RFe ions and neutrals were elucidated by a variety of tandem mass spectrometry techniques. The present study provides the first experimental evidence of the intrinsic stability of neutral IFe, NCFe, acacFe and C6H5Fe.
HawkerP.H.TwiggM.V., “Iron(II) and lower states”, in Comprehensive Coordination Chemistry, Volume 4, Ed by WilkinsonG.GillardR.D.McClevertyJ.A., Pergamon Press, Oxford, UK, p. 1179 (1987).
2.
MuradE., “Thermochemical properties of gaseous iron(II) oxide and iron hydroxide (FeOH)”, J. Chem. Phys.73, 1381 (1980).
3.
GorokhovL.N.RyzhovM.Yu.KhodeevYu.S., “Heats of formation of gaseous iron and magnesium fluorides (FeF, FeF2, MgF)”, Zh. Fiz. Khim.59, 2939 (1985).
4.
GorokhovL.M.MilushinM.I.EmelyanovA.M., “Knudsen effusion mass spectrometric determination of metal hydroxide stabilities”, High Temp. Sci.26, 395 (1990).
5.
KermodeS.M.BrownJ.M., “Identification of new low-lying electronic states of the FeF radical”, J. Mol. Spectrosc.213, 158 (2002).
6.
ReddyS.P., “New band systems of FeBr in the visible region”, J. Sci. Industrial Res.18B, 188 (1959).
7.
DelavalJ.M.DufourC.SchampsJ., “Rotational analysis of ultraviolet systems of iron monochloride radical”, J. Phys. B.13, 4757 (1980).
8.
KarrassS.SchwarzH., “Metal ion mediated heterocyclic cleavage of silicon–carbon bonds resulting in the generation of neutral MCH3 [metal–methyl] fragments (M = iron, cobalt)”, Int. J. Mass Spectrom. Ion Processes98, R1 (1990).
9.
RamR.S.BernathP.F.DavisS.P., “Fourier transform emission spectroscopy of the g4Δ-a4Δ system of FeF”, J. Mol. Spectrosc.179, 282 (1996).
10.
BeatonS.P.EvensonK.M.NelisT.BrownJ.M., “Detection of the free radicals iron hydride, cobalt hydride, and nickel hydride (FeH, CoH, and NiH) by far infrared laser magnetic resonance”, J. Chem. Phys.89, 4446 (1988).
11.
PasternakM.Van der HeydenM.LangoucheG., “The characterization of iron hydride (FeH) molecules by Moessbauer spectroscopy”, Chem. Phys. Lett.104, 398 (1984).
12.
AllenM.D.ZiurysL.M., “Millimeter-wave spectroscopy of FeF (X6?i): Rotational analysis and bonding study”, J. Chem. Phys.106, 3494 (1997).
13.
AllenM.D.LiB.Z.ZiurysL.M., “A multimeter/submillimeter-wave spectroscopic study of the FeCl radical (X6Δi)”, Chem. Phys. Lett.270, 517 (1997).
14.
TanimotoM.SaitoS.OkabayashiT., “Microwave spectrum of FeCl radical in the electronic ground 6Δi state”, Chem. Phys. Lett.242, 153 (1995).
15.
RamR.S.BernathP.F., “Fourier transform spectroscopy of the g4Δ-a4Δ system of FeCl”, J. Mol. Spectrosc.221, 261 (2003).
16.
RaoN.V.K.RaoP.T., “New band system of the iron bromide [FeBr] molecule”, J. Phys. B: Atom. Mol. Phys.3, 725 (1970).
17.
BarrettP.H.PasternakM., “A Moessbauer study of iron bonding to solid ammonia and its photofragments”, J. Chem. Phys.71, 3837 (1979).
18.
LanghoffS.R.BauschlicherC.W.Jr, “Theoretical study of the spectroscopy of FeH”, J. Mol. Spectrosc.141, 243 (1990).
19.
BauschlicherC.W.Jr, “The dissociation energies of FeF, FeCl, and FeBr and their positive ions”, Chem. Phys.211, 163 (1996).
20.
McKeeM.L., “Ab initio study of the interaction of Fe, Fe+, and HFe with H, CH, CH2, CH3, and C5H5”, J. Am. Chem. Soc.112, 2601 (1990).
21.
BachR.D.ShobeD.S.SchlegelH.B.NagelC.J., “Thermochemistry of iron chlorides and their positive and negative ions”, J. Phys. Chem.100, 8770 (1996).
22.
ElasserC.KrimmelH.FahnieM.LouieS.G.ChanC.T., “Ab initio of iron and iron hydride. III. Vibrational states of H isotopes in Fe, Cr, and Ni”, J. Phys.: Condens. Mat.10, 5131 (1998).
23.
FawzyD.E.YousselN.H.EngvoldO., “Identification of FeH molecular lines in the spectrum of a sunspot umbra”, Astron. Astrophys., Suppl. Ser.129, 435 (1998).
24.
NordhH.L.LindgrenB.WingR.F., “A proposed identification of FeH in the spectra of M dwarfs and S stars”, Astron. Astrophys.56, 1 (1977).
25.
CleggR.E.S.LambertD.L., “On the identification of iron Hydride (FeH) and cerium oxide in S stars”, Astrophys. J.226, 931 (1978).
26.
WingR.F.CohenJ.BraultJ.W., “Confirmation of the presence of iron hydride in sunspots and cool stars”, Astrophys. J.216, 659 (1977).
27.
DendramisA.van ZeeR.J.WeltnerW.Jr, “The iron hydride (FeH) molecule at 4 K”, Astrophys. J.231, 632 (1979).
28.
ChertihinG.V.AndrewsL., “Infrared spectra of FeH, FeH2, and FeH3 in solid argon”, J. Phys. Chem.99, 12131 (1995).
29.
DeVoreT.C.Van ZeeR.J.WeltnerW.Jr, “An investigation of the first row transition-metal fluoride molecules using ESR spectroscopy”, Proceedings Electrochem. Society, p. 187 (1978).
30.
WesdemiotisC., “Neutralization-reionization in mass spectrometry”, in Encyclopedia of Spectroscopy and Spectrometry, Ed by LindonJ.C.TranterG.E.HolmesJ.L., Academic Press, San Diego, CA, USA, p. 1469 (2000).
31.
WesdemiotisC.McLaffertyF.W., “Neutralization-reionization mass spectrometry (NRMS)”, Chem. Rev.87, 485 (1987).
32.
TerlouwT.J.SchwarzH., “Gasification and characterization of molecules by neutralization–reionization-mass spectrometry (NRMS)”, Angew. Chem. Int. Ed. Engl.26, 805 (1987).
33.
HolmesJ.L., “The neutralization of organic cations”, Mass Spectrom. Rev.8, 513 (1989).
34.
SchwarzH., “Generation of elusive neutrals and dications by neutralization resp. Charge stripping of monocations in beam experiments”, Pure Appl. Chem.61, 685 (1981).
35.
McLaffertyF.W., “Studies of unusual simple molecules by neutralization–reionization mass spectrometry”, Science247, 925 (1990).
36.
ZagorevskiiD.V.HolmesJ.L., “Neutralization-reionization mass spectrometry applied to organometallic and coordination chemistry”, Mass Spectrom. Rev.13, 133 (1994).
37.
ZagorevskiiD.V.HolmesJ.L., “Neutralization-reionization mass spectrometry applied to organometallic and coordination chemistry (Update: 1994–1998)”, Mass Spectrom. Rev.18, 87, (1999).
38.
ZagorevskiiD.V., “The generation and characterization of elusive metal complexes in the gas phase: Neutralization–reionization mass spectrometry and related experiments”, Coord. Chem. Rev.225, 5 (2002).
39.
ZagorevskiiD.V., “The generation of elusive metal complexes by neutralization–reionization mass spectrometry (NRMS)”, in Encyclopedia of Mass SpectrometryVolume 4, Ed by GrossM.L.CaprioliR.M.NibberingN.M.M., Elsevier, Amsterdam, The Netherlands, p. 702 (2005).
40.
SchroderD.BarschS.SchwarzH., “Redox properties of charged and neutral iron chlorides FeClmn (m =1–3; n = −1,0,+1, and +2)”, Int. J. Mass Spectrom.192, 125 (1999).
41.
LebrillaC.B.DrewelloT.SchwarzH., “Formation and detection of neutral FeCHx (x = 0–3) using neutralization–reionization mass spectrometry (NRMS)”, Organometallics6, 2268 (1987).
42.
DrewelloT.SchwarzH., “Generation and characterization of stable monomeric transition metal acetylides MCCH (M = Fe, Co, Ni) by neutralization–reionization mass spectrometry”, Chem. Phys. Lett.171, 5 (1990).
43.
SchroderD.SchwarzH., “Generation of cationic and neutral iron formate, HCOOFe, in the gas phase”, Organometallics11, 2296 (1992).
44.
FiedlerA.SchroderD.SchwarzH.TjeltaB.L.ArmentroutP.B., ““Bare” Iron Methoxide Cation: A Simple Model To Probe the Mechanism of β-Hydrogen Transfer in Organometallic Compounds”, J. Am. Chem. Soc.118, 5047 (1996).
45.
DrewelloT.SchwarzH., “Formation and detection of neutral half-sandwich complexes MC5H5(M = Fe, Co, Ni) using neutralization–reionization mass spectrometry (NRMS)”, Int. J. Mass Spectrom. Ion Processes93, 177 (1989).
46.
ZagorevskiiD.V.HolmesJ.L.ZverevD.OrlovaT.Yu.NekrasovYu.S., “The structure of C5H5RFe+ (R = F, Cl, Br, I, O, OH, OCH3, C6H5, H) ions in the gas phase and the generation of their neutral counterparts by neutralization–reionization mass spectrometry”, J. Am. Soc. Mass Spectrom.6, 1143 (1995).
47.
BruceM.I., “Electron-impact studies of organometallic molecules, III. Some carbonylmetal halides and cyclopentadienyls”, Int. J. Mass Spectrom. Ion Phys.1, 141 (1968).
48.
BeranováŠ.WesdemiotisC., “Internal energy distributions of tungsten hexacarbonyl ions after neutralization–reionization”, J. Am. Soc. Mass Spectrom.5, 1093 (1994).
49.
CzaboA.WilhelmiH., “Mechanism of steel surface in d.c. glow discharge”, Haerterei-Tech. Mitt.39, 148 (1984).
50.
EllerK.SülzleD.SchwarzH., “On the generation and identification of stable HCN/Cu(0) and HNC/Cu(0) complexes in the gas phase using neutralization–reionization mass spectrometry (NRMS)”, Chem. Phys. Lett.154, 443 (1989).
51.
ReichertC.WestmoreJ.B., “Mass spectral studies of metal chelates, IV. Mass spectra, appearance potentials, and coordinate bond energies of bis(acetylacetonate)metal(II) complexes of the first transition series”, Inorg. Chem.8, 1012 (1969).
52.
SchröderD.HrušákJ.SchwarzH., “Ligand effects on the reactivity of iron(II) cations FeX+ in the gas phase”, Ber. Bunsen-Ges. Phys. Chem.97, 1085 (1993).
53.
SchultzR.H.ArmentroutP.B., “The gas-phase thermochemistry of FeH”, J. Chem. Phys.94, 2262 (1991).
54.
GradeM.RosingerW., “A mass spectrometric investigation of iron(II)-iodide”, Ber. Bunsen-Ges. Phys. Chem.88, 767 (1984).
