scispace - formally typeset
Search or ask a question

Showing papers by "Bruce S. Ault published in 1987"




Journal ArticleDOI
TL;DR: In this paper, the formation of 1:1 molecular complexes of ClF and Cl/sub 2/ with dimethyl sulfide and related bases has been investigated, and the infrared spectra of the complexes were dominated by an intense absorption which has been assigned to the perturbed halogen stretching mode.
Abstract: Matrix isolation has been coupled with twin jet deposition for the formation of 1:1 molecular complexes of ClF and Cl/sub 2/ with dimethyl sulfide and related bases. The infrared spectra of the complexes were dominated by an intense absorption which has been assigned to the perturbed halogen stretching mode. This mode was greatly intensified and red-shifted upon complex formation; the observed shifts of up to 300 cm/sup -1/ were much greater than shifts for the complexes of CIF with oxygen bases. The spectral differences have been rationalized in terms of hard/soft acid/base theory. Visible-ultraviolet spectra were also recorded for these complexes at high dilutions; for several an intense charge-transfer band was observed in the UV. Mercury arc irradiation into this charge-transfer absorption led to photochemically induced rearrangement reactions for several of the complexes studied.

17 citations


Journal ArticleDOI
TL;DR: In this article, the authors used infrared spectroscopy coupled with matrix isolation technique for a study of the molecular complexes formed between SO/sub 3/ and soft Lewis bases (phosphorus and sulfur bases), each 1:1 complex was characterized by a significant shift of the antisymmetric stretching mode of the SO subunit as well as by the perturbation of certain base vibrational modes.
Abstract: Infrared spectroscopy has been coupled with the matrix isolation technique for a study of the molecular complexes formed between SO/sub 3/ and soft Lewis bases (phosphorus and sulfur bases). Each 1:1 complex was characterized by a significant shift of the antisymmetric stretching mode of the SO/sub 3/ subunit as well as by the perturbation of certain base vibrational modes. The shifts observed in this study were substantially larger than those seen in previous studies of the complexes of SO/sub 2/ with oxygen and nitrogen bases. This is in disagreement with predictions based on the proton affinity of the base, but fits well with the principles of hard/soft acid/base theory. The data are also in good agreement with the extensive data on HF complexes of similar bases.

13 citations



Journal ArticleDOI
TL;DR: In this paper, the matrix isolation technique has been employed in an attempt to characterize intermediates formed during pyrolysis of B 2 H 6 and O 2, which is likely that elemental boron and H 2 are the dominant products.

9 citations


Journal ArticleDOI
TL;DR: In this article, an excimer laser operating at 193 nm was coupled with the matrix isolation technique for the synthesis of chemical intermediates, which yielded CH 4 and H 2 CNCH 3 upon irradiation, likely by the photodetachment of a methyl group followed by hydrogen atom abstract within the matrix cage.

7 citations


Journal ArticleDOI
TL;DR: In this article, the matrix isolation technique has been employed in conjunction with infrared spectroscopy to study the interaction of cyclopropane with the Lewis acids BF 3, BCl 3, BBr 3, SiF 4, and GeF 4.

5 citations


Journal ArticleDOI
TL;DR: In this paper, the matrix isolation technique has been employed to isolate and characterize complexes of the hydrogen halides with cyclobutane, cyclopentane and cyclohexane.

4 citations



Journal ArticleDOI
TL;DR: In this paper, the matrix isolation technique has been employed for the study of the interaction between several Lewis acids and Cr(CO) 6 and Mo(CO), and the results showed that the singlet jet codeposition of either BF 3 or BCl 3 with these metal carbonyls gave no indication of complex formation.

Journal ArticleDOI
TL;DR: In this paper, the matrix isolation technique has been employed for the study of the interaction between several Lewis acids and Cr(CO) 6 and Mo(CO), and the results showed that the singlet jet codeposition of either BF 3 or BCl 3 with these metal carbonyls gave no indication of complex formation.
Abstract: The matrix isolation technique has been employed for the study of the interaction between several Lewis acids and Cr(CO) 6 and Mo(CO) 6 . The twin jet codeposition of ClF with either of the metal hexacarbonyls gave rise to a single product absorption at 1974 cm −1 , which is indicative of a perturbed carbonyl stretching mode in a weakly bound molecular complex. No perturbed mode of the ClF subunit was detected, contrary to previous ClF studies. The singlet jet codeposition of either BF 3 or BCl 3 with these metal carbonyls gave no indication of complex formation. These results are discussed, as is the potential implication for Lewis acid-induced alkyl migration reactions.

Journal ArticleDOI
TL;DR: In this paper, the matrix isolation technique has been employed in an attempt to characterize intermediates formed during pyrolysis of B 2 H 6 and O 2, which is likely that elemental boron and H 2 are the dominant products.
Abstract: The matrix isolation technique has been employed in an attempt to characterize intermediates formed during the pyrolysis and pyrolytic oxidation of B 2 H 6 . Samples were passed through a pyrolysis zone heated to as high as 350°C. When no oxygen was present, complete decomposition of the parent diborane was observed, with no new product species. Under these conditions, it is likely that elemental boron and H 2 are the dominant products. Pyrolysis of samples containing B 2 H 6 and O 2 led to a strong absorption near 1380 cm −1 , which is assigned by comparison to literature spectra to boroxin, H 3 B 3 O 3 . 18 O Data have been obtained for the latter species and are used to support a D 3h structure for the compound.