Flow Tube Kinetic Study of Mo and Mo2 Reactivity

Li, Lian; Mitchell, S. A.; Rayner, D. M.

doi:10.1021/j100096a004

Cited by 69 publications

(73 citation statements)

References 8 publications

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“…The 3 AЉ structure was calculated to be bound by 32.4 (CP corrected value: 30.8) kcal/mol with respect to the fragment ground states. The formation of the 3 AЉ complex causes an increase in both the C-C and Mo-Mo bond lengths (0.1 Å) and a tilting angle (38°) with respect to free fragments.…”

Section: Mo-and Mo 2 -C 2 H 4 Complexesmentioning

confidence: 99%

“…The interaction between Mo 1,2 and a -donor ligand (NH 3 ) results into the formation of the spin-conserved complexes ( 7 A 1 and 1 AЈ for Mo-NH 3 and Mo 2 -NH 3 , respectively) compared to the spin multiplicity of the ground state of the metal center. Contrarily, in the case of a -acceptor ligand (such as C 2 H 2 or C 2 H 4 ), the spin multiplicity changes upon complexation: low-spin state ( 5 B 2 ) for the 1-1 complex and high-spin state ( 3 AЉ) for the 2-1 complexes.…”

Section: Mo-and Mo 2 -C 2 H 4 Complexesmentioning

confidence: 99%

“…There is neither a change in the number of basins (7) nor in their synaptic order. That means that two fragment reducible domains, one for Mo the other for NH 3 , split for a value defining the bounding isosurface lower than that of the core-valence separation (see Scheme I).…”

Section: -1 Complexesmentioning

confidence: 99%

“…1,2 Previous experimental [3][4][5] and theoretical works 6 -8 indicate that transition metal atoms and dimers show sometimes remarkable differences in reactivity with respect to adduct formation reactions depending on the electron acceptor/donor capabilities of the ligand. In the case of Lewis base ligands, an increase of reactivity in going from the atom to the dimer has been observed, whereas for -acceptor ligands, the opposite behavior has been manifested.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13][14][15][16][17] In addition, it has been experimentally established 3 that Mo atoms form bounded complexes with C 2 H 4 but not with NH 3 , whereas the reverse situation characterizes the dimer reactivity. This behavior has been previously attributed 3 to the modified bonding capabilities of the clusters, which, as a consequence of the intermetallic bond, are able to reduce electronic repulsion effects that restrict the reactivity of atoms. In clusters, this type of repulsion can be indeed alleviated by means of polarization mechanisms that are unavailable in the case of atoms.…”

Section: Introductionmentioning

confidence: 99%

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Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules

Michelini¹,

Russo²,

Alikhani³

et al. 2004

J Comput Chem

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The Density functional theory has been applied to characterize the structural features of Mo(1,2)-NH(3),-C(2)H(4), and -C(2)H(2) compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo(1,2)-NH(3)), the interaction between Mo (or Mo(2)) and C(2)H(4) (or C(2)H(2)) are the low-spin (Mo-C(2)H(4) and -C(2)H(2)) and high-spin (Mo(2)-C(2)H(4) and -C(2)H(2)) complexes. In the ground state of Mo(1,2)-C(2)H(4) and -C(2)H(2), the metal-center always reacts with the C-C center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a pi-acceptor ligand correlates with a maximum charge transfer from the metal center to the C-C bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the C-C basin. The interaction between Mo(1,2) and C(2)H(4) (or C(2)H(2)) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo(1,2) and NH(3), and the partners are bound by an electrostatic interaction.

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Section: Mo-and Mo 2 -C 2 H 4 Complexesmentioning

confidence: 99%

Section: Mo-and Mo 2 -C 2 H 4 Complexesmentioning

confidence: 99%

Section: -1 Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules

Michelini¹,

Russo²,

Alikhani³

et al. 2004

J Comput Chem

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Depletion kinetics of low-lying states of tungsten in the presence of NO, N2O, and SO2

Harter

Campbell

McClean

1997

Int. J. Chem. Kinet.

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The gas-phase reactivities of W(a 5 D J , a 7 S 3 ) with N 2 O, SO 2 , and NO in the temperature range of 295 -573 K are reported. Tungsten atoms were produced by the photodissociation of W(CO) 6 . The tungsten atoms were detected by a laser-induced fluorescence technique. The removal rate constants for the 6s 2 5d 4 a 5 D J states were found to be J dependent for all of the reactants. Removal rate constants for the 6s 1 5d 5 a 7 S 3 state were found to be fast compared to the a 5 D J states and often approached the gas kinetic rate constant. The reaction rates for all the states were found to be pressure independent with respect to the total pressure. Results are discussed in terms of the different electronic configurations of the states of tungsten.

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Lewis Acid‐Mediated One‐Electron Reduction of Nitrous Oxide

Liu

Solari

Scopelliti

et al. 2018

Chemistry A European J

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The one‐electron reduction of nitrous oxide (N2O) was achieved using strong Lewis acids E(C6F5)3 (E=B or Al) in combination with metallocenes. In the case of B(C6F5)3, electron transfer to N2O required a powerful reducing agent such as Cp*2Co (Cp*=pentamethylcyclopentadienyl). In the presence of Al(C6F5)3, on the other hand, the reactions could be performed with weaker reducing agents such as Cp*2Fe or Cp2Fe (Cp=cyclopentadienyl). The Lewis acid‐mediated electron transfer from the metallocene to N2O resulted in cleavage of the N−O bond, generating N2 and the oxyl radical anion [OE(C6F5)3]⋅−. The latter is highly reactive and engages in C−H activation reactions. It was possible to trap the radical by addition of the Gomberg dimer, which acts as a source of the trityl radical.

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Flow Tube Kinetic Study of Mo and Mo2 Reactivity

Cited by 69 publications

References 8 publications

Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules

Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules

Depletion kinetics of low-lying states of tungsten in the presence of NO, N2O, and SO2

Lewis Acid‐Mediated One‐Electron Reduction of Nitrous Oxide

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Flow Tube Kinetic Study of Mo and Mo2 Reactivity

Cited by 69 publications

References 8 publications

Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 molecules

Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 molecules

Depletion kinetics of low-lying states of tungsten in the presence of NO, N2O, and SO2

Lewis Acid‐Mediated One‐Electron Reduction of Nitrous Oxide

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Product

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Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules

Energetic and topological analysis of the reaction of Mo and Mo₂ with NH₃, C₂H₂, and C₂H₄ molecules