Showing papers by "Bruce S. Ault published in 2005"
TL;DR: Wavelength dependence studies determined that light of lambda < 590 nm led to reaction and oxygen atom transfer, forming an eta(1)-complex between 2,4-cyclohexadienone and CrCl(2)O.
Abstract: The matrix isolation technique, combined with infrared spectroscopy, has been used to characterize the products of the photochemical reactions of benzene with CrCl2O2 and OVCl3. While initial twin jet deposition of the reagents led to no visible changes in the recorded spectra, strong product bands were noted following irradiation with light of λ > 300 nm. Wavelength dependence studies determined that light of λ < 590 nm led to reaction and oxygen atom transfer, forming an η1-complex between 2,4-cyclohexadienone and CrCl2O. The identification of the complex was further supported by isotopic labeling (13C and 2H) and by density functional calculations at the B3LYP/6-311G++(d,2p) level. Merged-jet experiments in which thermal reactions are examined were also conducted, at temperatures as high as 150 °C. No products were observed.
13 citations
TL;DR: In this article, the matrix isolation technique has been combined with Vis/UV spectroscopy to characterize electronic transitions in 1:1 complexes of OVCl 3 with a series of lone pair electron donors.
11 citations
TL;DR: In this article, the matrix isolation technique was combined with UV/Visible spectroscopy to characterize electronic transitions in 1:1 complexes of CrO2Cl2 with a series of lone pair electron donors.
9 citations
TL;DR: In this article, the matrix isolation technique was combined with theoretical calculations to identify and characterize the photoproducts in the reactions of CH 3 CN with CrCl 2 O 2 and OVCl 3.
8 citations
TL;DR: Theoretical calculations indicated that the acetyl chloride derivative was approximately 10 kcal/mol more stable than the corresponding chloroacetaldehyde species for each system at the B3LYP/6-311++g(d,2p) level of theory.
Abstract: The matrix-isolation technique has been combined with infrared spectroscopy to identify and characterize the products formed by irradiation of cage-paired CrCl2O2 and a series of chloroethenes, C2HxCly (x + y = 4) For each system, oxygen-atom transfer occurred upon irradiation, yielding the corresponding acetyl chloride derivative and the Cl2CrO species The products were formed in the same matrix cage and strongly interacted to form a distinct molecular complex after formation Three different modes of interaction were explored computationally: η1 to the oxygen atom, η2 to the CO bond, and η1 to the chlorine atom In addition, a five-membered metallocycle and the chloroepoxide species were considered No evidence was obtained for the chloroacetaldehyde derivative, indicating the occurrence of oxygen-atom attack at the more substituted carbon of the chloroethene Evidence tentatively supporting the formation of the metallocycle was obtained as well Theoretical calculations indicated that the acetyl chl
6 citations
TL;DR: In this paper, the matrix isolation technique combined with infrared spectroscopy and theoretical calculations was employed to explore the reaction chemistry of the VCl 4 /(CH 3 ) 2 CO system, which was characterized by strongly shifted C O and VCl stretching modes, as well as by lesser perturbations to additional modes of acetone.
1 citations