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Fe+ Chemistry

EXPLANATION OF table

This is a compilation of rate constants and product distributions for positive ion/molecule reactions involving iron which have been measured with the selected-ion flow tube (SIFT) technique in the Ion Chemistry Laboratory at York University up to 2005.

The table is ordered according to the molecular weight of the reactant ion in the chemical equation. When reactant ions are the same, the reactions are ordered according to the neutral reactant. This latter procedure is based upon counting the number of carbon and hydrogen atoms in the neutral reactant. First priority is given to the number of carbon atoms. The greater the number of carbon atoms, the further down the table the neutral will appear. Within groups of neutrals containing the same number of carbon atoms, the order is determined by the number of hydrogen atoms. If the molecules contain the same number of hydrogen atoms, then the order is dependent alphabetically on the remaining atoms in the neutral. Neutral reactants that do not contain carbon atoms are ordered alphabetically with the earliest letter taking precedence, and precede carbon-containing molecules. In cases where the early letter is the same, the ordering is done by molecular weight with the lower molecular weight taking precedence.

The collision rate constants included in the tabulation, kc, are derived using the combined variational transition-classical trajectory treatment of T. Su and W.J. Chesnavich, J. Chem. Phys., 76, 5183 (1982). Rate constants are presented in units of 10-9 cm3 molecule-1s-1 and are either bimolecular or pseudo-bimolecular. Reactions leading to association were not investigated as a function of total pressure. The experiments were conducted as 296 ± 2K using the SIFT technique in a Helium buffer gas at ca. 0.35 Torr or 1.15 × 1016 helium atoms cm-3.
REACTANTS PRODUCTS BR kexp kc kexp/kc References
 
Fe+            
             
HCN Fe+(HCN) 1 1.5×10-5 3.3 4.5×10-3 1
CH4 Fe(CH4)+ 1 <5×10-5 1.1 <5×10-5 3
CO NR 1 <1×10-5 0.76 <1.3×10-5 1,4
CO2 NR 1 <1×10-6 0.8 <1.25×10-6 1
C2H2 Fe(C2H2)+ 1 0.016 1.1 0.015 3
C2H4 Fe(C2H4)+ 1 0.061 1.1 0.055 3
C2H6 Fe(C2H6)+ 1 0.014 1.1 0.013 3
C3H4 (allene) Fe(C3H4)+ 1 0.21 1.2 0.18 3
C3H4 (propyne) Fe(C3H4)+ 1 0.7 1.5 0.47 3
C3H6 (propene) Fe(C3H6)+ 1 0.39 1.3 0.3 3
C3H8 Fe(C3H8)+ 1 0.39 1.2 0.33 3
C4H2 (diacetylene) Fe(C4H2)+ 1 0.35 1.2 0.29 3
C4H6(1,3-butadiene) Fe(C3H6)+ + C 1 0.84 1.3 0.65 3
i-C4H8 (isobutene) Fe(C4H8)+ 1 0.89 1.4 0.64 3
C4H10 Fe(C4H10)+ 0.4 1 1.2 0.83  
  Fe(C2H4)+ + C2H6 0.38        
  Fe(C3H6)+ + C1H4 0.13        
  Fe(C4H8)+ + H2 0.09        
D2 NR 1 <1×10-4 1.1 <9.09×10-5 1
HD NR 1 <1×10-4 1.2 <8.33×10-5 1
H2 NR 1 <1×10-5 1.5 <6.67×10-6 1
H2O NR 1 <1×10-4 2.4 <4.2×10-5 1
NO NR 1 <0.01 0.73 <0.014 1
NO2 FeO+ + NO 1 0.48 ± 0.04 0.89 0.54 1
N2 NR 1 <1×10-5 0.72 <1.39×10-5 1,2
N2O FeO+ + N2 1 0.031 ± 0.001 0.86 0.036 1
O2 NR 1 <1×10-5 0.66 <1.5×10-5 1
Fe(CH4)   1     0.82  
             
(c-C5H5)Fe+            
H2 (c-C5H5)Fe(H2)+ 1 3.6×10-4 0.15 0.0024 5
H2O (c-C5H5)Fe(H2O)+ 1 0.24 0.23 1 5
NH3 (c-C5H5)Fe(NH3)+ 1 1.6 2 0.8 5
CO (c-C5H5)Fe(CO)+ 1 0.11 0.72 0.15 5
N2 (c-C5H5)Fe(N2)+ 1 0.022 0.65 0.034 5
NO (c-C5H5)Fe(NO)+ 1 0.18 0.66 0.27 5
CO2 (c-C5H5)Fe(CO2)+ 1 0.23 0.68 0.34 5
N2O (c-C5H5)Fe(N2O)+ 1 0.25 0.74 0.34 5
NO2 (c-C5H5)FeO+ + NO 0.85 0.45 0.78 0.58 5
  (c-C5H5)Fe(NO2)+ 0.15        
             
             
Fe(C2H2)+            
C2H2 Fe(C2H2)2+ 1 0.77     3
             
Fe(C2H4)+            
CO   1 0.054 ± 0.002 0.74   4
C2H4 Fe(C2H4)2+ 1 0.63     3
N2O   1 0.12 ± 0.01 0.79   4
             
Fe(C2H6)+            
C2H6 Fe(C2H6)2+ 1 0.37     3
             
Fe(C3H4)+            
C3H4 (allene) Fe(C3H4)2+ 1 0.6     3
             
Fe(C3H4)+            
C3H4 (propyne) Fe(C3H4)2+ 1 0.75     3
             
Fe(C3H6)+            
C3H6 (propene) Fe(C3H6)2+ 1 0.39     3
             
Fe(C3H8)+            
C3H8 Fe(C3H8)2+ 1 0.73     3
             
Fe(C4H2)+            
C4H2 (diacetylene) Fe(C4H2)2+ 1 1     3
             
Fe(C2H2)2+            
C2H2 Fe(C2H2)3+ 1 0.76     3
             
Fe(C4H6)+            
C4H6 Fe(C4H6)2+ 1 0.85     3
             
Fe(C2H4)2+            
C2H4 Fe(C2H4)3+ 1 0.087     3
             
Fe(C4H8)+            
i-C4H8 (isobutene) Fe(C4H8)2+ 1 1.1     3
             
Fe(C4H10)+            
C4H10 Fe(C4H10)2+ 1 0.78     3
             
Fe(C2H6)2+            
C2H6 NR 1 <0.00005     3
             
Fe(c-C5H5)+            
CO   1 0.11 ± 0.01 0.71   4
N2   1 0.022 0.65   2
N2O   1 0.25 ± 0.01 0.75   4
             
Fe(C2H2)3+            
C2H2 Fe(C2H2)4+ 1 0.002 ± 0.001     3
             
Fe(C6H6)+            
CO   1 0.27 ± 0.04 0.7   4
N2   1 0.015 0.64   2
N2O   1 0.33 ± 0.03 0.74   4
             
Fe(C3H4)2+            
C3H4 (allene) Fe(C3H4)3+ 1 0.22     3
             
Fe(C3H4)2+            
C3H4 (propyne) Fe(C3H4)3+ 1 0.6     3
D2   1        
C2H4 Fe(C2H4)4+ 1 0.0003 ± 0.00015     3
             
Fe(C3H6)2+            
C3H6 (propene) Fe(C3H6)3+ 1 0.33     3
             
Fe(C3H8)2+            
C3H8 NR 1 <0.00005     3
             
Fe(C4H2)2+            
C4H2 (diacetylene) Fe(C4H2)3+ 1 0.3      
             
Fe(C2H2)4+            
C2H2 Fe(C2H2)5+ 1 0.005 ± 0.002     3
             
Fe(C4H6)2+            
C4H6 Fe(C4H6)3+ 1 0.0033     3
             
Fe(C2H4)4+            
C2H4   1 not observed     3
             
Fe(C4H8)2+            
i-C4H8 (isobutene) Fe(C4H8)3+ 1 0.0053     3
             
Fe(C4H10)2+            
C4H10 NR 1 <0.0001     3
             
Fe(C3H4)3+            
C3H4 (allene) NR 1 <0.0001     3
             
Fe(C3H4)3+            
C3H4 (propyne) Fe(C3H4)4+ 1 0.006 ± 0.003     3
             
Fe(C3H6)3+            
C3H6 (propene) NR 1 <0.0001     3
             
Fe(C2H2)5+            
C2H2 Fe(C2H2)6+ 1 observed     3
             
Fe(c-C5H5)2+            
N2   1 < 0.00001 0.63   2
             
Fe(C4H2)3+            
C4H2 (diacetylene) Fe(C4H2)4+ 1 0.009 ± 0.005     3
             
Fe(C2H2)6+            
C2H2   1 not observed     3
             
Fe(C6H6)2+            
N2   1 <0.0001 0.62   2
             
Fe(C3H4)4+            
C3H4 (propyne) Fe(C3H4)5+ 1 0.007 ± 0.004     3
             
Fe(C4H6)3+            
C4H6 (1,3-butadiene) Fe(C4H6)4+ 1 observed     3
             
Fe(C4H8)3+            
i-C4H8 (isobutene) NR 1 <0.0001     3
             
Fe(C3H4)5+            
C3H4 (propyne) Fe(C3H4)6+ 1 observed     3
             
Fe(C4H2)4+            
C4H2 (diacetylene) Fe(C4H2)5+ 1 0.01 ± 0.005     3
             
Fe(C4H6)4+            
C4H6   1 not observed     3
             
Fe(C3H4)6+            
C3H4 (propyne)   1 not observed     3
             
Fe(C4H2)5+            
C4H2 (diacetylene) Fe(C4H2)6+ 1 observed     3
             
Fe(C4H2)6+            
CO   1 0.13 ± 0.01 0.65   4
CO Fe+ + CO2 1 0.21 ± 0.02 0.73   1
CO2 FeO(CO2)+ 1 0.0049 ± 0.0004 0.76   1
C4H2 (diacetylene)   1 not observed     3
D2 Fe+ + D2O 1 0.0042 ± 0.0003 1.1   1
Fe(C60)+   1        
FeO+   1        
HD Fe+ + HDO 1 0.0077 ± 0.0003 1.2   1
H2 Fe+ + H2O 1 0.0088 ± 0.0002 1.5   1
H2O FeO(H2O)+ 1 0.18 ± 0.02 2.4   1
NO NR 1 <0.01 0.7   1
NO2 NO+ + FeO2 1 0.49 ± 0.04 0.84   1
N2 FeO(N2)+ 1 0.00005 ± 0.00003 0.69   1,2
N2O FeO(N2O)+ 1 0.012 ± 0.001 0.81   1
N2O   1 0.17 ± 0.02 0.66   4
O2 NR 1 <0.00002 0.63   1
             
FeO(CO2)+            
CO2 FeO(CO2)2+ 1 0.0037     1
             
FeO(CO2)2+            
CO2 FeO(CO2)3+ 1 0.0002     1
             
FeO(CO2)3+            
CO2 NR 1 0.000001     1
             
FeO(H2O)+            
H2O FeO(H2O)2+ 1 0.28     1
             
FeO(H2O)2+            
H2O FeO(H2O)3+ 1 0.2     1
             
FeO(H2O)3+            
H2O FeO(H2O)4+ 1 0.05     1
             
FeO(H2O)4+            
H2O FeO(H2O)5+ 1 0.05     1
             
FeO(N2)+            
N2 FeO(N2)2+ 1 ≤ 1×10-5 0.66 ≤ 1.5×10-5 2
             
FeO(N2)2+            
N2   1 < 1×10-5 0.645 < 1.6×10-5 2
             
FeO(N2O)+            
N2O FeO(N2O)2+ 1 0.012     1
             
FeO(N2O)2+            
N2O FeO(N2O)3+ 1 0.014     1
             
FeO(N2O)3+            
N2O NR 1 <0.00001     1
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References [1] Fullerometallic Ion Chemistry: Reactions of C60Fe+ and C20H10Fe+ in the Gas Phase.
D. Caraiman, G. Koyanagi, L.T. Scott, D.V. Preda and D.K. Bohme, J. Am. Chem. Soc., 123, 8573-8582 (2001).

[2] Coordination Chemistry of Fe+, (c-C5H5)Fe+ and (c-C5H5)2Fe+ in the Gas-Phase at Room Temperature: Kinetics of Sequential Ligation with Hydrogen Cyanide and Cyanoacetylene.
V. Baranov and D.K. Bohme, Int. J. Mass Spectrom., 210/11, 303-310 (2001).

[3] Intrinsic Coordination Properties of Iron: Gas-Phase Ligation of Ground-State Fe+ with Alkanes, Alkenes, and Alkynes and Intramolecular Interligand Interactions Mediated by Fe+.
V. Baranov, H. Becker and D.K. Bohme, J. Phys. Chem. 101, 5137-47 (1997).

[4] Reactions of Fe+ Coordinated to the π-Donating Ligands C2H4, c-C5H5, C6H6 and C60 with N2O and CO: Probing the Bonding in (C60)Fe+.
V.I. Baranov and D.K. Bohme. Int. J. Mass Spectrom. Ion Processes, 149/150, 543-555 (1995).

[5] Coordination chemistry of (c-C5H5)Fe+ in the gas phase at 294±3 K: reactions with inorganic ligands H2, H2O, NH3, CO, N2, NO, CO2, N2O, and NO2.
Vladimir Baranov, Diethard K. Bohme, International Journal of Mass Spectrometry 204. 209-221 (2000).
Ion Chemistry Laboratory, York University 4700 Keele Street, Toronto, Ontario M3J 1P3