Metal atoms as superbases: the gas phase proton affinity of uranium

Armentrout, P. B.; Hodges, Ronald V.; Beauchamp, J. L.

doi:10.1021/ja00451a051

Cited by 41 publications

(31 citation statements)

References 1 publication

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“…Anions, on the other hand, can have extremely large electron affinities, as one expects . As early as in 1976, Armentrout and co‐workers pointed out that metal atoms can be very strong bases in the gas phase . In fact, both the coordinated metal and the coordinating ligand in a metal complex may compete for the preferred protonation site (ligand protonation is mostly preferred, though).…”

Section: Methodsmentioning

confidence: 99%

Tipping the Balance between Ligand and Metal Protonation due to Relativistic Effects: Unusually High Proton Affinity in Gold(I) Pincer Complexes

Jerabek

Vondung

Schwerdtfeger

2018

Chemistry A European J

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Quantum theoretical studies show that the extremely high proton affinity at the metal center of the unusual T-shaped (LXL)Au -pincer complex, consisting of a carbazole framework and two mesoionic carbenes, is caused by relativistic effects. This brings the basicity of the Au center in line with the electron-rich nitrogen atom of the carbazole ring system, resulting in one of the highest proton affinities for a neutral molecule.

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Section: Methodsmentioning

confidence: 99%

Tipping the Balance between Ligand and Metal Protonation due to Relativistic Effects: Unusually High Proton Affinity in Gold(I) Pincer Complexes

Jerabek

Vondung

Schwerdtfeger

2018

Chemistry A European J

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“…Higher energies were required for C-H bond activation by oxidative addition to the metal center to form AuH + + CH 3 and AuCH 3 + + H products. [27][28][29][30] and there are now numerous experimental studies of the reactions of the ions of atomic first-row transition metals, [31][32][33][34][35][36][37][38][39][40][41] second-row transition metals, 39,40,42,44 third-row transition metals, 42,45,48 and other metals, [49][50][51][52][53] with dihydrogen, reaction (1), and its isotopic analogs, HD and D 2 25,26 To investigate this process in the absence of competing processes, the present work examines the activation of dihydrogen.…”

Section: Introductionmentioning

confidence: 99%

Guided ion beam and theoretical study of the reactions of Au+ with H2, D2, and HD

Hinton

Citir

et al. 2011

The Journal of Chemical Physics

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Reactions of the late third-row transition metal cation Au(+) with H(2), D(2), and HD are examined using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au(+) in its (1)S (5d(10)) electronic ground state level. Corresponding state-specific reaction cross sections for forming AuH(+) and AuD(+) as a function of kinetic energy are obtained and analyzed to give a 0 K bond dissociation energy of D(0)(Au(+)-H) = 2.13 ± 0.11 eV. Quantum chemical calculations at the B3LYP∕HW+∕6-311+G(3p) and B3LYP∕Def2TZVPP levels performed here show good agreement with the experimental bond energy. Theory also provides the electronic structures of these species and the reactive potential energy surfaces. We also compare this third-row transition metal system with previous results for analogous reactions of the first-row and second-row congeners, Cu(+) and Ag(+). We find that Au(+) has a stronger M(+)-H bond, which can be explained by the lanthanide contraction and relativistic effects that alter the relative size of the valence s and d orbitals. Results from reactions with HD provide insight into the reaction mechanism and indicate that ground state Au(+) reacts largely via a direct mechanism, in concordance with the behavior of the lighter group 11 metal ions, but includes more statistical behavior than these metals as well.

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“…This is one of the simplest reactions and therefore potentially among the most useful because it can be studied in detail both experimentally and theoretically. The periodic trends in such bond activation chemistry are particularly interesting, [3][4][5] and there are now numerous experimental studies of the reactions of the ions of atomic first-row transition metals, [6][7][8][9][10][11] second-row transition metals, 6,7,[11][12][13] thirdrow transition metals, 11,[14][15][16][17][18][19] and other metals [20][21][22][23][24] with dihydrogen, reaction (1), and its isotopic analogues.…”

Section: Introductionmentioning

confidence: 99%

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Hinton

Citir

Armentrout

2011

The Journal of Chemical Physics

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Reactions of the third-row transition metal cation Os(+) with H(2), D(2), and HD to form OsH(+) (OsD(+)) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os(+) in its (6)D (6s(1)5d(6)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH(+) and OsD(+) are analyzed to give a 0 K bond dissociation energy of D(0)(Os(+)-H) = 2.45 ± 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os(+) reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe(+) and Ru(+), and find that Os(+) reacts more efficiently with dihydrogen, forming a stronger M(+)-H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.

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Metal atoms as superbases: the gas phase proton affinity of uranium

Cited by 41 publications

References 1 publication

Tipping the Balance between Ligand and Metal Protonation due to Relativistic Effects: Unusually High Proton Affinity in Gold(I) Pincer Complexes

Tipping the Balance between Ligand and Metal Protonation due to Relativistic Effects: Unusually High Proton Affinity in Gold(I) Pincer Complexes

Guided ion beam and theoretical study of the reactions of Au+ with H2, D2, and HD

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

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