We investigate the photochemistry and photodissociation dynamics of the linear C3H2 isomer propadienylidene by two-colour photofragment Doppler spectroscopy at excitation wavelengths between 260 and 230 nm, corresponding to excitation into the C1 A1 state. Propadienylidene is generated by pyrolysis from IC3H2Br. Almost complete conversion of the precursor can only be achieved at high pyrolysis temperatures. Two reaction channels, H-atom loss and loss of H2 molecules, are energetically close. Our results show that H-atom loss is indeed important in the investigated energy range. The Doppler profiles indicate that 34-37% of the excess energy is released as translation. The rates for H-atom loss are faster than the time resolution of our nanosecond-laser setup, kH > 10(8) s(-1).
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http://dx.doi.org/10.1039/b807049k | DOI Listing |
Phys Chem Chem Phys
October 2024
Department of Chemistry, University of California at Riverside, Riverside, CA 92521, USA.
The ultraviolet (UV) photodissociation dynamics of the 2-buten-2-yl (CH) radical were studied using the high- Rydberg atom time-of-flight (HRTOF) technique in the photolysis region of 226-246 nm. 2-Buten-2-yl radicals were generated by 193 nm photodissociation of the precursor 2-chloro-2-butene. The H-atom photofragment yield (PFY) spectrum of 2-buten-2-yl is broad, peaking at 234 nm.
View Article and Find Full Text PDFJ Phys Chem A
July 2024
Department of Chemistry, University of California at Riverside, Riverside, California 92521, United States.
The ultraviolet (UV) photodissociation dynamics of the 1-methylallyl (1-MA) radical were studied using the high- Rydberg atom time-of-flight (HRTOF) technique in the wavelength region of 226-244 nm. The 1-MA radicals were produced by 193 nm photodissociation of the 3-chloro-1-butene and 1-chloro-2-butene precursor. The 1 + 1 REMPI spectrum of 1-MA agrees with the previous UV absorption spectrum in this wavelength region.
View Article and Find Full Text PDFDalton Trans
December 2024
Department of Chemistry, Rutgers University-Newark, 73 Warren Street, Newark, NJ 07102, USA.
The coordination chemistry of an amine-rich Cp ligand has been explored with cobalt. We demonstrate that in the presence of NaCo(CO), the cationic precursor [CpN3]+ yields the complex CpN3CoI(CO)2. While 2e oxidation generates new Co complexes such as [CpN3Co(NCMe)3]2+ and CpN3CoI2(CO), subsequent ligand loss is facile, generating free [CpN3]+ or the protonated dication [CpN3H]2+.
View Article and Find Full Text PDFEur J Mass Spectrom (Chichester)
June 2024
Department of Chemistry, University of California, Riverside, CA, USA.
Thermal decomposition and isomerization of 1-butyl and 1-pentyl radical were studied in the temperature range of 500-1480 K on a short time scale of 20-100 µs using flash pyrolysis vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry. 1-Bromobutane and 1-bromopentane were used as precursors for the 1-butyl and 1-pentyl radical, respectively. The reactive intermediates in the thermal dissociation reactions were directly observed.
View Article and Find Full Text PDFOrg Lett
May 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, UP-208016, India.
Herein we report a visible-light-induced, α-aminoalkyl radical-mediated cascade reaction of 1,7-enynes that establishes a unique ring-closing enyne transformation pathway which occurs with concomitant loss of a methylene moiety. The α-aminoalkyl radical derived from ,-dimethylaniline was demonstrated to be a traceless promoter of enyne reorganization leading to 4-alkylquinolinones. The reaction can also be extended to nitrile-substituted acrylamide systems, leading to carbostyrils.
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