Reactions of atomic metal ions with alkyl halides and alcohols in the gas phase

Allison, John; Ridge, D. P.

doi:10.1021/ja00511a033

Cited by 177 publications

(124 citation statements)

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“…The traditional reaction mechanism of a side-on complex involves C-C bond insertion followed by P-H shift and competitive ligand elimination, as first suggested by Allison and Ridge (21,22). A similar reaction mechanism has been established for the side-on complexes of RCN-Cu+ (19).…”

Section: Fragmentations Of Adductsmentioning

confidence: 67%

Ion–molecule reactions of transition-metal ions with nitriles in the gas phase: competitive formation of both "end-on" and "side-on" coordination

Chen¹,

Miller²

1991

Can. J. Chem.

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LIN-ZHI CHEN and JACK M. MILLER. Can. J. Chem. 69,2002Chem. 69, (1991. First field-free region B/E linked scan studies of metastable and particularly collision-induced dissociations show that two competitive coordination processes ("end-on" and "side-on") exist in the complexation of metal ions (Ni+, Co+, Fe+, and Mn+) with alkanenitriles in the FAB source of an E/B configuration mass spectrometer. Analysis of the B/E linked scan CA spectra gives approximate percentages of the end-on coordination mode in the reactive complexes. An unusual @-methyl migration, involved in the elimination of CH, from end-on complexes, may be in competition with P-H migration/elimination of H2 and @-C-C bond cleavage/elimination of alkene. For the side-on complexes, the metal ions can insert into various C-C bonds followed by P-H transfer/competitive elimination of alkene and alkane or by a direct C-M+ bond cleavage to give an alkyl radical.Key words: FAB mass spectroscopy, metal-ion/nitrile reactions, collisional activation, coordination modes, ion-molecule reactions. [Traduit par la redaction] LIN-ZHI

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Section: Fragmentations Of Adductsmentioning

confidence: 67%

Ion–molecule reactions of transition-metal ions with nitriles in the gas phase: competitive formation of both "end-on" and "side-on" coordination

Chen¹,

Miller²

1991

Can. J. Chem.

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“…14,15 They observed that ion-molecule reactivity depended mainly on the halogenide or alcohol nature and also on the particular alkali ion, lithium being the most reactive. A possible reaction mechanism was proposed.…”

Section: Introductionmentioning

confidence: 99%

“…A possible reaction mechanism was proposed. 15 Using crossed beam techniques, Creasy and Farrar studied the dehydrohalogenation of some propyl chloride and propyl bromide isomers induced by collisions with low energy Li + , measuring branching ratios for different reaction channels 16 at fixed collision energies, and also the similarly induced t-butanol dehydration in the gas phase. 17 In our previous studies on ion-molecule dehydrohalogenation or dehydration reactions, [18][19][20][21][22] we reported excitation functions for different reaction channels including some for previously not-described reactions.…”

Section: Introductionmentioning

confidence: 99%

“…17 In our previous studies on ion-molecule dehydrohalogenation or dehydration reactions, [18][19][20][21][22] we reported excitation functions for different reaction channels including some for previously not-described reactions. [14][15][16][17] These studies were complemented by ab initio calculations with which it proved possible to characterize the stationary points associated with the different reaction channels in the ground singlet state potential energy surface (PES) on which the adiabatic reactive processes took place at low collision energies. It is a well-known fact that alkali ions, on colliding with neutral molecules at low enough pressure, can form stable ion-molecule adducts, 23 and in fact our experiments in single collision conditions clearly confirm such formation of an adduct before the system evolves to products where the alkali ion is coordinated either with the unsaturated hydrocarbon or with the removed molecule.…”

Section: Introductionmentioning

confidence: 99%

“…[24][25][26] To the best of our knowledge, neither reaction (3) nor (4) for the systems reported here has been described in the bibliography, nor were reactions (2) and (3) observed in earlier studies of the same. 14,15 In this work in Section II a brief description on the experimental setup and the details of the quantum chemistry calculations are given. The experimental and computational results for the Li + + i-C 3 H 7 Br dehydrohalogenation reactions are shown in Section III, while Section IV reports on the equivalent information for the Li + + i-C 3 H 7 OH dehydration reaction.…”

Section: Introductionmentioning

confidence: 99%

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The role of Li+ ions in the gas phase dehydrohalogenation and dehydration reactions of i-C3H7Br and i-C3H7OH molecules studied by radiofrequency-guided ion beam techniques and ab initio methods

Lopez

Lucas

Andrés

et al. 2017

The Journal of Chemical Physics

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Gas phase reactive collisions between lithium ions and i-C3H7X (X = Br, OH) molecules have been studied under single collision conditions in the center of mass (CM) 0.01-10.00 eV energy range using a radiofrequency-guided ion beam apparatus. Mass spectrometry analysis of the products did show the presence of [C3H6—Li]+, [HX—Li]+, C3H7+, and C2H3+ as well as of the [Li—i-C3H7Br]+ adduct while [Li—i-C3H7OH]+ was hardly detected. For all these reactive processes, the corresponding cross sections have been measured in absolute units as a function of the CM collision energy. Quantum chemistry ab initio calculations done at the second order Möller Plesset level have provided relevant information on the topology of the potential energy surfaces (PESs) where a reaction takes place allowing the characterization of the stationary points on the respective PESs along their reaction pathways. The connectivity of the different stationary points localized on the PESs was ensured by using the intrinsic reaction coordinate (IRC) method, confirming the adiabatic character of the reactions. The main topology features of the reactive PESs, in the absence of dynamical calculations, were used to interpret at the qualitative level the behavior of the experimental excitations functions, evidencing the role played by the potential energy barriers on the experimental dynamics of the reactions. Reaction rate constants at 303.2 K for different reactions have been calculated from measured excitation functions.

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Inherent Asymmetry of Constitutionally Equivalent Methyl Groups in the H/D Equilibration ofn- andi-C3H7Fe(OH)+ Complexes

et al. 2001

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Reactions of atomic metal ions with alkyl halides and alcohols in the gas phase

Cited by 177 publications

References 3 publications

Ion–molecule reactions of transition-metal ions with nitriles in the gas phase: competitive formation of both "end-on" and "side-on" coordination

Ion–molecule reactions of transition-metal ions with nitriles in the gas phase: competitive formation of both "end-on" and "side-on" coordination

The role of Li+ ions in the gas phase dehydrohalogenation and dehydration reactions of i-C3H7Br and i-C3H7OH molecules studied by radiofrequency-guided ion beam techniques and ab initio methods

Inherent Asymmetry of Constitutionally Equivalent Methyl Groups in the H/D Equilibration ofn- andi-C3H7Fe(OH)+ Complexes

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