Activation of Molecular Hydrogen by Arylcarbenes

Enrique Mendez-Vega; Mika Maehara; Akshay Hemant Raut; Joel Mieres-Perez; Masashi Tsuge; Yuan-Pern Lee; Wolfram Sander

doi:10.1002/chem.201804657

Activation of Molecular Hydrogen by Arylcarbenes

Enrique Mendez-Vega, Mika Maehara, Akshay Hemant Raut, Joel Mieres-Perez, Masashi Tsuge, Yuan-Pern Lee^*, Wolfram Sander

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H₂ and D₂ matrices and in H₂- and D₂-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H₂ increases in the order 1<3<2. Whereas 1 is stable in solid H₂, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D₂ both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.

Original language	English
Pages (from-to)	18801-18808
Number of pages	8
Journal	Chemistry - A European Journal
Volume	24
Issue number	70
DOIs	https://doi.org/10.1002/chem.201804657
State	Published - 12 Dec 2018

Keywords

IR spectroscopy
carbenes
hydrogen activation
matrix isolation
tunneling

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title = "Activation of Molecular Hydrogen by Arylcarbenes",

abstract = "The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H2 and D2 matrices and in H2- and D2-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H2 increases in the order 1<3<2. Whereas 1 is stable in solid H2, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D2 both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.",

keywords = "IR spectroscopy, carbenes, hydrogen activation, matrix isolation, tunneling",

author = "Enrique Mendez-Vega and Mika Maehara and Raut, {Akshay Hemant} and Joel Mieres-Perez and Masashi Tsuge and Yuan-Pern Lee and Wolfram Sander",

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AU - Mendez-Vega, Enrique

AU - Maehara, Mika

AU - Raut, Akshay Hemant

AU - Mieres-Perez, Joel

AU - Tsuge, Masashi

AU - Lee, Yuan-Pern

AU - Sander, Wolfram

PY - 2018/12/12

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N2 - The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H2 and D2 matrices and in H2- and D2-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H2 increases in the order 1<3<2. Whereas 1 is stable in solid H2, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D2 both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.

AB - The hydrogenation reactions of diphenylcarbene 1, fluorenylidene 2, and dibenzocycloheptadienylidene 3 were investigated in solid H2 and D2 matrices and in H2- and D2-doped argon matrices at cryogenic temperatures. The reactivity of the carbenes towards H2 increases in the order 1<3<2. Whereas 1 is stable in solid H2, 2 and 3 react fast under the same conditions via quantum chemical tunneling. In D2 both 1 and 3 are stable, whereas 2 slowly reacts. The different reactivity of the three carbenes is rationalized in terms of differing carbene stabilization energies.

KW - IR spectroscopy

KW - carbenes

KW - hydrogen activation

KW - matrix isolation

KW - tunneling

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SP - 18801

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JO - Chemistry - A European Journal

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ER -

Activation of Molecular Hydrogen by Arylcarbenes

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