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Journal ArticleDOI

Matrix isolation investigation of the vibrational and electronic spectroscopy and photochemistry of complexes of chlorine fluoride and molecular chlorine with sulfide bases

Nicholas P. Machara, +1 more
- 09 Apr 1987 - 
- Vol. 91, Iss: 8, pp 2046-2050
TLDR
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.

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Journal ArticleDOI

Präreaktive Komplexe der Dihalogene XY mit Lewis‐Basen B in der Gasphase: eine systematische Studie der Halogen‐Analoga B⋅⋅⋅XY der Wasserstoffbrückenbindungen B⋅⋅⋅HX

TL;DR: In this article, the authors describe the abgebildeten Strukturen von Oxiran and ClF in der Gasphase, in denen B eine einfache Lewis-Base, XY ein Homo- oder Heterodihalogen-and HX ein Halogenwasserstoffmolekul ist.
Journal ArticleDOI

Effects of fluorine substitution on hydrogen bond interactions

TL;DR: The effect of fluorine substitution on a series of hydrogen-bonded (HB) systems has been studied with the aid of theoretical ab initio methods in this article, which indicates a 0.1 − 1 − 1−kcal/mol increase for the interaction energy.
Journal ArticleDOI

Main group coordination chemistry at low temperatures: A review of matrix isolated Group 12 to Group 18 complexes

TL;DR: The available data on main group (Groups 12-18) Lewis acid base, donor-acceptor, charge transfer and van der Waals complexes stabilised by matrix isolation techniques are presented, tabulated and evaluated in conjunction with data from complementary gas phase experiments and computational chemistry as discussed by the authors.
Journal ArticleDOI

Matrix isolation studies of reactive intermediate complexes

TL;DR: In this paper, a composes d'addition formes entre acides and bases of Lewis, par exemple SiF 4 •NH 3, are presented.
Journal ArticleDOI

FTIR matrix isolation studies of complexes of dimethylsulfide, dimethyldisulfide and hydrogen sulfide with nitric acid

TL;DR: In this paper, the strength of interaction between DMS, DMDS, and H 2 S with nitric acid has been investigated in argon and nitrogen matrices, showing that in all studied systems the HNO 3 molecule is hydrogen bonded to the base molecule.
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