Activation of Methane by Gas-Phase Rh+

Chen, Yu Min; Armentrout, P. B.

doi:10.1021/j100027a016

Cited by 101 publications

(145 citation statements)

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“…Such ion beam studies also provide insight into the electronic requirements for the activation of methane by transition metal ions and periodic trends in this reactivity. We have applied this methodology to all the first-row and second-row transition metals except Tc [3,[7][8][9][10][11][12][13][14][15][16][17][18] and more recently to several of the third-row metals as well [18][19][20][21]. A significant advantage of these comprehensive studies is the comparison of bond energies and reactivities of all transition-metal complexes, thereby establishing periodic trends.…”

Section: Introductionmentioning

confidence: 99%

The most reactive third-row transition metal: Guided ion beam and theoretical studies of the activation of methane by Ir+

Li¹,

Zhang²,

Armentrout³

2006

International Journal of Mass Spectrometry

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Section: Introductionmentioning

confidence: 99%

The most reactive third-row transition metal: Guided ion beam and theoretical studies of the activation of methane by Ir+

Li¹,

Zhang²,

Armentrout³

2006

International Journal of Mass Spectrometry

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“…There is a growing body of experimental information regarding the interactions of small neutral 1 and cationic [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] clusters of transition metals with compounds containing prototypical bonds ͑e.g., C-H, C-C, N-H, O-H, Si-H, Si-C͒ of importance in catalytic processes. Transition metal-main group complexes have been the focus of intense computational effort.…”

Section: Introductionmentioning

confidence: 99%

An ab initio study of the reaction mechanism of Co++NH3

Taketsugu

Gordon

1997

The Journal of Chemical Physics

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To investigate the mechanism for N-H bond activation by a transition metal, the reactions of Co+(3F,5F) with NH3 have been studied with complete active space self-consistent field (CASSCF), multireference configuration interaction (MR-SDCI), and multireference many body perturbation theory (MRMP) wave functions, using both effective core potential and all-electron methods. Upon their initial approach, the reactants yield an ion-molecule complex, CoNH+3(3E,5A2,5A1), with retention of C3ν symmetry. The Co+=NH3 binding energies are estimated to be 49 (triplet) and 45 (quintet) kcal/mol. Subsequently, the N-H bond is activated, leading to an intermediate complex H-Co-NH+2 (C2ν symmetry), through a threecenter transition state with an energy barrier of 56-60 (triplet) and 70-73 (quintet) kcal/mol. The energy of H-Co-NH+2, relative to that of CoNH+3, is estimated to be 60 to 61 (triplet) and 44 (quintet) kcal/mol. However, the highest levels of theory employed here (including dynamic correlation corrections) suggest that the triplet intermediate HCoNH+2 may not exist as a minimum on the potential energy surface. Following Co-N or H-Co bond cleavage, the complexH-Co-NH+2 leads to HCo++NH2 or H+CoNH+2. Both channels (triplet and quintet) are found to be endothermic by 54-64 kcal/mol. Theoretical study of the water activation by a cobalt cation: Ab initio multireference theory versus density functional theory

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“…Charges of rhodium and rhodium oxide play significant roles in controlling their catalytic activity and selectivity. With regard to C-H bond activation by related rhodium compound in the gas phase, the neutral rhodium atom is able to activate the C-H bond of methane under mild conditions [49,50], while rhodium ion and related rhodium compounds exhibit fine performances on the C-H bond activation of hydrocarbon [51][52][53]. As mentioned earlier, the methane activation by the neutral RhO has been studied theoretically, where the main products shall be Rh ?…”

Section: )mentioning

confidence: 99%