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Cyclobutadienes conformation

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). [Pg.75]

Cycloalkenes, into if-allyl palladium complexes, 8, 363 Cycloalkenyl rings, metal complex conformational interconversions, 1, 414 Cycloalkynes, in nickel complexes, 8, 147 (Cyclobutadiene)cyclopentadienyl complexes, with cobalt, polymercuration, 2, 435 Cyclobutadienes... [Pg.89]

Cyclooctatetraene would be antiaromatic if Htickel s rule applied, so the conjugation of its double bonds is energetically unfavorable. Remember that Htickel s rule applies to a compound only if there is a continuous ring of overlapping p orbitals, usually in a planar system. Cyclooctatetraene is more flexible than cyclobutadiene, and it assumes a nonplanar tub conformation that avoids most of the overlap between adjacent pi bonds. Hiickel s rule simply does not apply. [Pg.723]

In the case of the square conformation of cyclobutadiene, the energy levels would be... [Pg.520]

Cyclooctatetraene In accord with the Hiickel rule of 4/i -h 2 electrons, both cyclobutadiene and cyclooc-and Cyclobutadiene tatetraene (cot) are nonaromatic. Cyclooctatetraene contains alternating bond lengths Complexes bd has a tub-shaped conformation ... [Pg.354]

The smallest conceivable conjugated monocyclic diene is 1,3-cyclobutadiene. Several complexes involving cyclobutadiene are known. The compound itself is unstable and has not been studied by structural methods. It will therefore not be included in the present discussion. 1,3-Cyclobutadiene has, however, been isolated in argon matrices, and it has been established that the molecule has symmetry. For the tetra-tert-butyl derivative an envelope conformation (twist angle 7°) was found by X-ray methods, however the distances in the ring were obviously too similar for an antiaromatic system [1.464(3) and 1.483(3) A]. A redetermination at even lower temperatures gave more reasonable results (1.441 and 1.527 A) and a further analysis of the anisotropic parameters revealed that some residual disorder is still responsible for some equilibration and distances of 1.34 and 1.60 A were assumed to be the correct ones. ... [Pg.37]

One of the most intriguing successes of simple MO theory is the prediction of nonexistence of a number of jt-electron systems. Chemical existence is a very difficult notion which includes thermodynamic and kinetic requirements 108), so that predictions obtained from MO theory must be interpreted rather cautiously. Since it is assumed that -electron systems are planar (or nearly so), any considerable deviation from planarity can alter the theoretical predictions. For example, cyclo-octatetraene (which is predicted to be a rather unstable compound) and its derivatives are well defined compounds, but have nonplanar (a puckered T>2a tub ) conformation io9,no) it is this escape from planarity which makes cyclooctatetraene a stable compound. Other compounds, may exist as highly reactive species, as is the case with cyclobutadiene iii.ua) and its derivatives 118>. [Pg.72]

The size of the K-system chosen has important implication on the structural and functional aspects of metal binding. To explore the size effect calculations were performed on the cation-ir complexes of Li+ and Mg + with the Jt-face of linear and cyclic unsaturated hydrocarbons [45]. In the case of the acyclic Jt-systems, we started with the simplest system, e.g. ethylene followed by buta-1,3-diene, hexa-l,3,5-triene, and octa-1,3,5, 7-tetraene with 2, 3 and 4, conjugated jt units, respectively. These linear systems with two and more number of jt units can have various conformations wherein the jt units can have cis, trans or a combination of both cis and trans orientations. Similarly for cyclic systems cyclobutadiene, benzene, cyclooctateraene, naphthalene, anthracene, phenanthrene and naphthacene have been included. Thus a wide range of sizes for aromatic systems have been covered. [Pg.528]

It suggests that it is not the size of the ring but the number of electrons present in it determines whether a molecule would be aromatic or antiaromatic. In fact the molecules with An+ 2) n electrons are aromatic whereas with (An, 0) n electrons are antiaromatic. Thus, benzene, cyclopropenyl cation, cyclobutadiene dication (or dianion), cyclopentadie-nyl anion, tropylium ion, cyclooctatetraene dication (or dianion), etc. possess (4 + 2) ti electrons and hence aromatic whereas cyclobutadiene, cyclopentadienyl cation, cycloheptatrienyl anion, cyclooctatetraene (non-planar) etc. have An n electrons which make them antiaromatic . Systems like [10] annulene are forced to adopt a nonplanar conformation due to transannular interaction between two hydrogen atoms and hence their aromaticity gets reduced even if they have (An + 2)n electrons. On the other hand the steric constraints in systems like cyclooctatetraene force it to adopt a tube-like non-planar conformation which in turn reduces its antiaromaticity. Various derivatives of benzene like phenol, toluene, aniline, nitrobenzene etc. are also aromatic where the benzene ring and the n sextet are preserved. In homoaromatic " systems, like cyclooctatrienyl cation, delocalization does not extend over the whole molecule. [Pg.54]

Cyclobutadiene is antiaromatic cyclooctatetraene adopts a tub-shaped conformation and is nonaromatic. [Pg.851]

Some structures of compounds [Fe(cyclobutadiene)L3] close to one of the idealized forms 13 or 14 are found but an analysis of known structures has shown no real angular preferences with structures being found with various conformations between 13 and 14. No case of a frozen-out nmr spectrum has been... [Pg.255]


See other pages where Cyclobutadienes conformation is mentioned: [Pg.58]    [Pg.38]    [Pg.255]    [Pg.37]    [Pg.887]    [Pg.381]    [Pg.555]    [Pg.631]    [Pg.555]    [Pg.154]    [Pg.521]    [Pg.1012]    [Pg.2053]    [Pg.194]    [Pg.631]    [Pg.339]    [Pg.555]    [Pg.887]    [Pg.896]    [Pg.462]    [Pg.887]    [Pg.2052]    [Pg.20]    [Pg.148]    [Pg.53]    [Pg.339]    [Pg.136]    [Pg.285]   
See also in sourсe #XX -- [ Pg.177 ]




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