118017-04-2Relevant academic research and scientific papers
Activation of Molecular Hydrogen by Arylcarbenes
Mendez-Vega, Enrique,Maehara, Mika,Raut, Akshay Hemant,Mieres-Perez, Joel,Tsuge, Masashi,Lee, Yuan-Pern,Sander, Wolfram
, p. 18801 - 18808 (2018/11/27)
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 12, 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.
Reaction of Diphenylmethylene and Phenylmethylene with Oxygen. A Matrix Isolation Study
Sander, Wolfram W.
, p. 333 - 339 (2007/10/02)
The thermal and photochemical reactions of phenylcarbene and diphenylcarbene in oxygen-doped matrices have been investigated.The primary thermal adducts of free carbenes and O2 are carbonyl O-oxides, which are characterized by IR and UV spectroscopy.Most characteristic are intense O-O stretching modes in the IR (ν=900 cm1-) and ?-->?* transitions in the UV (λ=400 nm) spectra.The carbonyl O-oxides are very photolabile toward long-wavelength irradiation (500-630 nm) and either rearrange to dioxiranes or split off oxygen atoms.The distribution of photoproductsis determined by substituents: benzophenone O-oxide mainly gives diphenyldioxirane while benzaldehyde O-oxide gives the aldehyde and oxygen atoms.The strong chemiluminescence observed during the thermal reaction is explained by the reaction of free carbenes and oxygen atoms forming a C=O bond in situ.This reaction is highly exothermic and produces carbonyl compounds in their triplet states.
