Primary Reaction of the Titanium-Catalyzed Oligomerization of Phosphorus in the Gas Phase

Irigoras, Arantxa; Fowler, and Joseph E.; Ugalde, Jesús M.

doi:10.1021/ja990726z

Cited by 36 publications

(88 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…16 O 2 (Linde, 99.9991%), 18 O 2 (Sigma-Aldrich, 99 atom %), Nitrous Oxide (Sigma-Aldrich, 99.0%), and CO 2 (Linde, 99.995%) were introduced into the ultra high vacuum region via a needle valve at constant pressures in the range of 5 × 10 −8 to 5 × 10 −7 mbar. Isotopically enriched targets were used where applicable, 52 Cr (99.9%), 56 Fe (99.7%), 58 Ni (99.9%), 63 Cu (99.3%), 64 Zn (99.4%) (STB Isotope Germany GmbH). Chromium was delivered as a sheet which was used directly.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

et al. 2012

View full text Add to dashboard Cite

The reactions of hydrated monovalent transition metal ions M(+)(H(2)O)(n), M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward molecular oxygen, nitrous oxide, and carbon dioxide were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Clusters containing monovalent chromium, cobalt, nickel, or zinc were reactive toward O(2), while only hydrated cobalt was reactive toward N(2)O. A strongly size dependent reactivity was observed. Chromium and cobalt react very slowly with carbon dioxide. Nanocalorimetric analysis, (18)O(2) exchange, and collision induced dissociation (CID) experiments were done to learn more about the structure of the O(2) products. The thermochemistry for cobalt, nickel, and zinc is comparable to the formation of O(2)(-) from hydrated electrons. These results suggest that cobalt, nickel, and zinc are forming M(2+)/O(2)(-) ion pairs in the cluster, while chromium rather forms a covalently bound dioxygen complex in large clusters, followed by an exothermic dioxide formation in clusters with n ≤ 5. The results show that hydrated singly charged transition metal ions exhibit highly specific reactivities toward O(2), N(2)O, and CO(2).

show abstract

Section: ■ Experimental Sectionmentioning

confidence: 99%

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

et al. 2012

View full text Add to dashboard Cite

show abstract

“…Larger systems were studied by the elimination of weakly bound second-sphere water molecules, providing a probe of progressive solvation . A number of theoretical studies have also explored singly charged cation–water complexes to complement these experiments. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Infrared Spectroscopy of Mn⁺(H₂O) and Mn²⁺(H₂O) via Argon Complex Predissociation

2011

View full text Add to dashboard Cite

Singly and doubly charged manganese-water cations, and their mixed complexes with attached argon atoms, are produced by laser vaporization in a pulsed nozzle source. Complexes of the form Mn(+)(H(2)O)Ar(n) (n = 1-4) and Mn(2+)(H(2)O)Ar(4) are studied via mass-selected infrared photodissociation spectroscopy, detected in the mass channels corresponding to the elimination of argon. Sharp resonances are detected for all complexes in the region of the symmetric and asymmetric stretch vibrations of water. With the guidance of density functional theory computations, specific vibrational band resonances are assigned to complexes having different argon attachment configurations. In the small singly charged complexes, argon adds first to the metal ion site and later in larger clusters to the hydrogens of water. The doubly charged complex has argon only on the metal ion. Vibrations in all of these complexes are shifted to lower frequencies than those of the free water molecule. These shifts are greater when argon is attached to hydrogen and also greater for the dication compared to the singly charged species. Cation binding also causes the IR intensities for water vibrations to be much greater than those of the free water molecule, and the relative intensities are greater for the symmetric stretch than the asymmetric stretch. This latter effect is also enhanced for the dication complex.

show abstract

“…14,15 In addition, state-specific comparisons have highlighted differences in the chemistry of Cu + ( 1 S) and Cu + ( 3 D). 16,17 Activation of the sigma bond in CH 4 represents the prototypical example of C−H bond activation and is the first step in the conversion of this abundant resource into more useful molecules. Numerous gas-phase studies of methane activation by transition-metal ions have revealed a wealth of mechanistic information regarding this important process.…”

Section: ■ Introductionmentioning

confidence: 99%

State-Specific Reactions of Cu⁺(¹S, ³D) with CH₃X and CF₃X (X = Cl, Br, I): Exploring the Influence of Dipole Orientation on Association and C–X Bond Activation

et al. 2012

View full text Add to dashboard Cite

The reactions of gas-phase Cu(+)((1)S) and Cu(+)((3)D) with CF(3)X and CH(3)X (X = Cl, Br, and I) have been examined experimentally using the drift cell technique at 3.5 Torr in He at room temperature. State-specific product channels and overall bimolecular rate constants for depletion of the two Cu(+) states were determined using electronic state chromatography. The results showed that Cu(+)((1)S) participates exclusively in association with all of these neutrals, whereas, depending on the neutral, Cu(+)((3)D) initiates up to three bimolecular processes, resulting in the formation of CuX(+), CuC(H/F)(3)(+), and C(H/F)(3)X(+). Possible structures for the singlet association products were explored using density functional methods. These calculations indicated that Cu(+) preferentially associates with the labile halogen (Cl, Br, I) with all neutrals except CF(3)Cl, for which a "backside" geometry occurs in which Cu(+)((1)S) is weakly bound to the -CF(3) end of the molecule. All products observed on the triplet reaction surface can be understood in terms of either known or calculated thermochemical requirements. Product distributions and overall reaction efficiencies for C-X bond activation (X = Br, I) through Cu(+)((3)D) suggest that the orientation of the neutral dipole has little or no effect in controlling access to specific product channels. Likewise, second-order rate constants for reactions with X = Br and I indicate efficient depletion of Cu(+)((3)D) and do not exhibit the dramatic variations in reaction efficiency previously observed with CH(3)Cl and CF(3)Cl. These results suggest that C-X bond activation proceeds through a bond-insertion mechanism as opposed to direct abstraction.

show abstract

Primary Reaction of the Titanium-Catalyzed Oligomerization of Phosphorus in the Gas Phase

Cited by 36 publications

References 27 publications

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Infrared Spectroscopy of Mn⁺(H₂O) and Mn²⁺(H₂O) via Argon Complex Predissociation

State-Specific Reactions of Cu⁺(¹S, ³D) with CH₃X and CF₃X (X = Cl, Br, I): Exploring the Influence of Dipole Orientation on Association and C–X Bond Activation

Contact Info

Product

Resources

About

Primary Reaction of the Titanium-Catalyzed Oligomerization of Phosphorus in the Gas Phase

Cited by 36 publications

References 27 publications

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M+(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M+(H2O)n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Infrared Spectroscopy of Mn+(H2O) and Mn2+(H2O) via Argon Complex Predissociation

State-Specific Reactions of Cu+(1S, 3D) with CH3X and CF3X (X = Cl, Br, I): Exploring the Influence of Dipole Orientation on Association and C–X Bond Activation

Contact Info

Product

Resources

About

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Reactivity of Hydrated Monovalent First Row Transition Metal Ions M⁺(H₂O)_n, M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide

Infrared Spectroscopy of Mn⁺(H₂O) and Mn²⁺(H₂O) via Argon Complex Predissociation

State-Specific Reactions of Cu⁺(¹S, ³D) with CH₃X and CF₃X (X = Cl, Br, I): Exploring the Influence of Dipole Orientation on Association and C–X Bond Activation