14067-02-8

Guided Ion Beam Studies of the State-Specific Reactions of Fe+(6D,4F) with CH3X (X = Cl, Br, I)

Fisher, Ellen R.,Schultz, Richard H.,Armentrout, P. B.

, p. 7382 - 7387 (1989)

Reactions of Fe+ with CH3X (X = Cl, Br, I) are studied by guided ion beam techniques.State-specific reaction cross sections for production of FeCH3+ and FeX+ are presented for the 6D ground and the 4F

112. Dichotomy of Fe+-Mediated Sequential Activation of C-H/C-C Bonds of Aldimines: A Case of Efficient Reaction Control by Chain-Length Effects

Pruesse, Tilmann,Schwarz, Helmut

, p. 1163 - 1166 (1990)

The metastable ions of Fe+ complexes of aldimines R1N=CHR2 exhibit a unique behaviour in that sequential loss of olefin/H2 follows two distinct pathways: one corresponds to the familiar pattern of double remote functionalization, involving either alkyl chain R1 and R2.In addition, based on labeling studies, evidence is presented demonstrating that the consecutive elimination of C2H4/H2 from the Fe+ complex of C6H13N=CHC3H7 involves exclusively the C6H13 part of the substrate.These and other Fe+-mediated C-H/C-C bond activations of aldimines are controlled by chain-lengths effects, reflecting the preferential formation of metallacyclic intermediates of particular ring sizes.

Vibrational spectroscopy and theory of Fe+(CH4) n (n = 1-4)

Citir, Murat,Altinay, Gokhan,Austein-Miller, Geoff,Metz, Ricardo B.

, p. 11322 - 11329 (2010)

Vibrational spectra are measured for Fe+(CH4) n (n = 1-4) in the C-H stretching region (2500-3200 cm-1) using photofragment spectroscopy. Spectra are obtained by monitoring CH 4 fragment loss following absorption of one photon (for n = 3, 4) or sequential absorption of multiple photons (for n = 1, 2). The spectra have a band near the position of the antisymmetric C-H stretch in isolated methane (3019 cm-1), along with bands extending >250 cm-1 to the red of the symmetric C-H stretch in methane (2917 cm-1). The spectra are sensitive to the ligand configuration (η2 vs η3) and to the Fe-C distance. Hybrid density functional theory calculations are used to identify possible structures and predict their vibrational spectra. The IR photodissociation spectrum shows that the Fe +(CH4) complex is a quartet, with an η3 configuration. There is also a small contribution to the spectrum from the metastable sextet η3 complex. The Fe+(CH 4)2 complex is also a quartet with both CH4 in an η3 configuration. For the larger clusters, the configuration switches from η3 to η2. In Fe+(CH 4)3, the methane ligands are not equivalent. Rather, there is one short and two long Fe-C bonds, and each methane is bound to the metal in an η2 configuration. For Fe+(CH4) 4, the calculations predict three low-lying structures, all with η2 binding of methane and very similar Fe-C bond lengths. No single structure reproduces the observed spectrum. The approximately tetrahedral C1 (4A) structure contributes to the spectrum; the nearly square-planar D2d (4B2) and the approximately tetrahedral C2 (4A) structure may contribute as well.

Transition-Metal Cation Chemistry in 1 Torr of He: M+ + C2H6 Reaction Rates

Tonkyn, Russ,Weisshaar, James C.

, p. 2305 - 2308 (1986)

We have used laser vaporization of solid metal targets to create first transition series gas-phase metal cations M+ in a fast flow reactor with 1 Torr of He buffer gas.In contrast with single-collision results, all ten first transition series M+ ions, Sc+ through Zn+, react with C2H6 in our multicollision experiment.The major primary product is usually the adduct ion MC2H6+ arising from third-body collisional stabilization of long-lived intermediates.The primary reaction rates vary a factor of 250 across the series.M+ ions having ground-state or low-energy 3dn electron configurations react the fastest with alkanes in 1 Torr of He.

Buckner, Steven W.,Freiser, Ben S.

, p. 1401 - 1406 (1989)

Reactions of Fe+ and FeO+ with C2H 2, C2H4, and C2H6: Temperature-dependent kinetics

Ard, Shaun G.,Melko, Joshua J.,Fournier, Joseph A.,Shuman, Nicholas S.,Viggiano, Albert A.

, p. 10178 - 10185 (2013/11/06)

We present the first temperature-dependent rate constants and branching ratios for the reactions of Fe+ and FeO+ with C 2H2, C2H4, and C2H 6 from 170 to 700 K. Fe

Iron-Mediated Cycloaddition of 1,3-Butadiene with Ethyne and Propyne in the Gas Phase

Bakhtiar, R.,Drader, J. J.,Jacobson, D. B.

, p. 8304 - 8306 (2007/10/02)

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