Matrix isolation

The molecular constants that describe the stnicture of a molecule can be measured using many optical teclmiques described in section A3.5.1 as long as the resolution is sufficient to separate the rovibrational states [110. 111 and 112]. Absorption spectroscopy is difficult with ions in the gas phase, hence many ion species have been first studied by matrix isolation methods [113], in which the IR spectrum is observed for ions trapped witliin a frozen noble gas on a liquid-helium cooled surface. The measured frequencies may be shifted as much as 1 % from gas phase values because of the weak interaction witli the matrix. 

Apkarian V A, Wiedman L, Janiesoh W and Weitz E 1986 Vibrational energy transfer and migration prooesses in matrix isolated CHjF J. Chem. Phys. 85 5593-610... 

Xenon dichloride [13780-38-6], XeCl, and xenon(II) chloroduoride [73378-52-6], XeClE, have been prepared by photochemical and electric discharge methods and have been examined at low temperatures by matrix-isolation techniques (39,40). The dichloride has a linear stmcture like that of XeE2. Evidence for the existence of XeCl2, XeBr2, and xenon tetrachloride [14989-42-5], XeCl, has been obtained from Mn ssbauer studies (41,42). Owing to thermal chemical instabiUties, no dihaUde other than the binary duorides has been prepared in macroscopic amounts. 

Shielding and Stabilization. Inclusion compounds may be used as sources and reservoirs of unstable species. The inner phases of inclusion compounds uniquely constrain guest movements, provide a medium for reactions, and shelter molecules that self-destmct in the bulk phase or transform and react under atmospheric conditions. Clathrate hosts have been shown to stabiLhe molecules in unusual conformations that can only be obtained in the host lattice (138) and to stabiLhe free radicals (139) and other reactive species (1) similar to the use of matrix isolation techniques. Inclusion compounds do, however, have the great advantage that they can be used over a relatively wide temperature range. Cyclobutadiene, pursued for over a century has been generated photochemicaHy inside a carcerand container (see (17) Fig. 5) where it is protected from dimerization and from reactants by its surrounding shell (140). 

IP, isolated pure MI, matrix isolated GP, data from pure gas phase material CE, chemical evidence for existence TH, theoretical calculation XR, X-ray structure MW, microwave structure UV ultraviolet spectrum. 

We may now be on the verge of the third phase of oxirene chemistry in which modern matrix isolation techniques (80CSR1) will permit the spectroscopic observation of this system, theory will serve as a guide to the synthesis of relatively stable oxirenes (c/. a fairly stable... 

An extensive series of low-temperature matrix isolation experiments has failed to provide any evidence of oxirene formation, either by diazo ketone photolysis (82CB2192) or by attempted photo-retro-cycloaddition (82CB2202). 

In the numerous studies of the IR-spectra of the matrix-isolated reactants (see, e.g., Frei and Pimentele [1983]) there have been found a number of chemical conversions. Among them, from the point of view of the present review, the reaction NO with O3 [Lucas and Pimentele 1979],... 

Either UV-VIS or IR spectroscopy can be combined with the technique of matrix isolation to detect and identify highly unstable intermediates. In this method, the intomediate is trapped in a solid inert matrix, usually one of the inert gases, at very low temperatures. Because each molecule is surrounded by inert gas atoms, there is no possiblity for intermolecular reactions and the rates of intramolecular reactions are slowed by the low temperature. Matrix isolation is a very useful method for characterizing intermediates in photochemical reactions. The method can also be used for gas-phase reactions which can be conducted in such a way that the intermediates can be rapidly condensed into the matrix. 

Preparation of pentalene is followed by immediate dimerization. Low-temperature photolysis produces a new species believed to be pentalene, but the compound reverts to dimer at — 100°C. The matrix-isolated monomer has been characterized spectroscopically. The results are in accord with the predicted lack of stabilization. ... 

The shapes of the monomeric molecules of the Group 2 halides (gas phase or matrix isolation) pose some interesting problems for those who are content with simple theories of bonding and molecular geometry. Thus, as expected on the basis of either sp hybridization or the... 

From the foregoing it is clear that BH3 is a fugitive reaction species it exists only at exceedingly low concentrations but can be isolated and studied using matrix isolation techniques. Thus it can be generated by thermal dissociation of loosely bound 1 1 adducts with Lewis bases, such as PF3.BH3, and its reactions studied. 1 The relative stability of the adducts L.BH3 has been determined from thermochemical and spectroscopic data and leads to the following unusual sequence ... 

The boron trihalides are volatile, highly reactive, monomeric molecular compounds which show no detectable tendency to dimerize (except perhaps in Kr matrix-isolation experiments at 20K). In... 

By contrast to the plethora of simple oxo-halides and thiohalides of P, the corresponding derivatives of P are fugitive species that require matrix isolation techniques for preparation and characterization ClPO, BrPO, FPS and BrPS all form non-linear triatomic molecules, as expected. The corresponding oxosulfide, BrP(0)S, and its thio-analogue, FP(S)S, have also recently been isolated. 

HOF was first identified by P. N. Noble and G. C. Pimentel in 1968 using matrix isolation techniques F2/H2O mixtures were frozen in solid... 

Sulfur bromides are but poorly characterized and there are few reliable data on them. SBr2 probably does not exist at room temperature but has been claimed as a matrix-isolated product when a mixture of S2Cl2/SCl2 Br2 Ar in the ratio 1 1 150 is passed through an 80-W microwave discharge and the product condensed on a Csl... 

Another way to improve the analysis of complex matrices can be the combination of a multidimensional system with information-rich spectral detection (31). The analysis of eucalyptus and cascarilla bark essential oils has been carried out with an MDGC instrument, coupling a fast second chromatograph with a matrix isolation infrared spectrometer. Eluents from the first column were heart-cut and transferred to a cryogenically cooled trap. The trap is then heated to re-inject the components into an analytical column of different selectivity for separation and subsequent detection. The problem of the mismatch between the speed of fast separation and the... 

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