Hydrocarbon nonalternant

Quaternization of harman (235) with ethyl bromoacetate, followed by cyclization of the pyridinium salt 236 with 1,2-cyclohexane-dione in refluxing ethanol yielded an ester which on hydrolysis gave the pseudo-cross-conjugated mesomeric betaine 237. Decarboxylation resulted in the formation of the alkaloid Sempervirine (238). The PCCMB 237 is isoconjugate with the 11/7-benzo[u]fluorene anion—an odd nonalternant hydrocarbon anion—and belongs to class 14 of heterocyclic mesomeric betaines (Scheme 78). 

Nonbenzenoid cyclic conjugated hydrocarbons are conveniently classified into two categories conjugated hydrocarbons composed of odd-membered rings called, in terminology of molecular orbital theory, nonalternant hydrocarbons, and cyclic polyenes currently known as annulenes. 

Of the fundamental nonalternant hydrocarbons, only two prototypes were known about fifteen years ago azulene (XI, Fig. 5), the molecular structure of which was determined by Pfau and Plattner and fulvene (XIX) synthesized by Thiec and Wiemann. Early in the 1960 s many other interesting prototypes have come to be synthesized. Doering succeeded in synthesizing heptafulvene (XX) fulvalene (XXI) and heptafulvalene (XXIII). Prinzbach and Rosswog reported the synthesis of sesquifulvalene (XXII). Preparation of a condensed bicyclic nonalternant hydrocarbon, heptalene (VII), was reported by Dauben and Bertelli . On the other hand, its 5-membered analogue, pentalene (I), has remained, up to the present, unvanquished to many attempts made by synthetic chemists. Very recently, de Mayo and his associates have succeeded in synthesizing its closest derivative, 1-methylpentalene. It is added in this connection that dimethyl derivatives of condensed tricyclic nonaltemant hydrocarbons composed of 5- and 7-membered rings (XIV and XV), known as Hafner s hydrocarbons, were synthesized by Hafner and Schneider already in 1958. 

The anomalously reduced stabilities of certain nonalternant hydrocarbons and higher members of [4n+2] annulenes arise from their seemingly peculiar geometrical structures in which a strong bond distortion often accompanied by a molecular-symmetry reduction occurs. 

A theoretical explanation for such an anomalous phenomenon in certain nonalternant hydrocarbons has first been attempted, in case of pentalene, by Boer-Veenendaal and Boer followed by Boer-Veenen-daal et Snyder and Nakajima and Katagiri for other related nonalternant hydrocarbons. By making allowance for the effects of <7-bond compression, these authors have shown that a distorted structure resembling either of the two Kekule-type structures is actually energetically favored as compared with the apparently-full symmetrical one. 

Using the above procedure and the A j, values, Binsch has examined the second-order bond fixations in the ground states of linear, cyclic, and benzenoid hydrocarbons and nonalternant hydrocarbons... 

Table 1. The second-order bond distortion in the ground states of nonalternant hydrocarbons...

Inspection of Table 2 reveals that all those molecules that suffer a molecular-symmetry reduction in the ground state possess (E2 — E1) values considerably larger than the critical value, so that they should have a fully-symmetrical nuclear configuration in their first excited states. On the other hand, there are cases where a molecule has an ( , — Eg) value significantly higher than the critical value, but has a relatively smaller (Ej— i) value. The ( 2 i) value of the pentalene dianion (I ) is of the same order of magnitude as the critical value and those for the peri-condensed nonalternant hydrocarbon, XVII, the fulvalenes, XXI, XXII and XXIII, and the dianions, IVand VII are significantly smaller than the critical value ( 0.6eV). 

Using the same method as described in II.B, Binsch and Heil-bronner have examined the second-order bond distortion in the lowest excited states of nonalternant hydrocarbons (I, IV—VII, X, XI, XIII — XV and XVII), and have shown that, of the molecules examined, only VI and XVII suffer a molecular-symmetry reduction in the lowest... 

The symmetry groups and bond lengths corresponding to the most stable nuclear configurations for nonalternant hydrocarbons and some of their dianions are shown in Fig. 5. 

On the other hand, in cata-condensed nonalternant hydrocarbons IV, VI, X and XI, peri-condensed nonalternant hydrocarbons XIV — XVIII, fulvenes XIX and XX, and fulvalenes XXI—XXIII, self-consistency was achieved only for the fully-symmetrical nuclear arrangement. All these molecule, except azulene pCl), also show in a greater or lesser degree a pronounced double-bond fixation. 

Of the cata-condensed nonalternant hydrocarbons undergoing a pseudo Jahn-Teller distortion, pentalene (I) and heptalene (VII), having the largest value, are predicted to possess a strong bond alternation. This confirms the results of the previous theoretical investi-gations " and agrees with the available experimental facts ... 

The anisotropy of the magnetic susceptibility of a cyclic conjugated system, attributable to induced ring currents in its rc-electron network, is one of the important quantities indicative of 7t-electron delocalization. The method used for the calculation of the magnetic susceptibilities of nonalternant hydrocarbons is the London-Hoarau method taken together with the Wheland-Mann SCF technique . The resonance integral is assumed again to be of exponential form but... 

In Table 5 are summarized theoretical lower-excitation energies and corresponding intensities for nonalternant hydrocarbons for which experimental data are available. Theoretical values are in general agreement with experimental ones. The predicted excitation energies for heptalene (VII) are rather small as compared with experimental data. This may arise as a consequence of nonplanarity due to the steric repulsions between ortho-hydrogen atoms. 

The results of our calculations based on both the static and dynamic theories show that most of the nonbenzenoid cyclic conjugated systems examined exhibit in a greater or lesser degree a marked double-bond fixation. The static theory indicates that even in benzene there exists a hidden tendency to distort into a skewed structure and that such a tendency is actually realized in [4n-f-2] annulenes larger than a certain critical size. In nonalternant hydrocarbons bond distortion is a rather common phenomenon. Fulvenes, fulvalenes and certain peri-condensed nonalternant hydrocarbons undergo a first-order bond distortion, and... 

Allyl (27, 60, 119-125) and benzyl (26, 27, 60, 121, 125-133) radicals have been studied intensively. Other theoretical studies have concerned pentadienyl (60,124), triphenylmethyl-type radicals (27), odd polyenes and odd a,w-diphenylpolyenes (60), radicals of the benzyl and phenalenyl types (60), cyclohexadienyl and a-hydronaphthyl (134), radical ions of nonalternant hydrocarbons (11, 135), radical anions derived from nitroso- and nitrobenzene, benzonitrile, and four polycyanobenzenes (10), anilino and phenoxyl radicals (130), tetramethyl-p-phenylenediamine radical cation (56), tetracyanoquinodi-methane radical anion (62), perfluoro-2,l,3-benzoselenadiazole radical anion (136), 0-protonated neutral aromatic ketyl radicals (137), benzene cation (138), benzene anion (139-141), paracyclophane radical anion (141), sulfur-containing conjugated radicals (142), nitrogen-containing violenes (143), and p-semi-quinones (17, 144, 145). Some representative results are presented in Figure 12. 

As mentioned for the relationship between the PE spectrum of a parent molecule and the electronic spectrum of its radical cation, any close correspondence between the electronic spectra of anions and cations or their hyperfine coupling patterns holds only for alternant hydrocarbons. The anions and cations of nonalternant hydrocarbons (e.g., azulene) have significantly different hyperfine patterns. Azulene radical anion has major hyperfine splitting constants (hfcs) on carbons 6, and 4,8 (flH = 0-91 mT, H-6 ah = 0-65 mT, H-4,8 ah = 0-38 mT, H-2) in contrast, the radical cation has major hfcs on carbons 1 and 3 (ah = 1.065 mT, H-1,3 Ah = 0.152 mT, H-2 ah = 0.415 mT, H-5,7 ah = 0.112 mT, H-6). °°... 

Aromatic hydrocarbons can be divided into two types. In alternant hydrocarbons, the conjugated carbon atoms can be divided into two sets such that no two atoms of the same set are directly linked. For convenience one set may be starred. Naphthalene is an alternant and azulene a nonalternant hydrocarbon ... 

The observed spectra of some duroquinone-nickel complexes with olefins have been correlated by means of semiquantitative molecular-orbital theory by Schrauzer and Thy ret (48). In the case of n complexes of polynuclear hydrocarbons, such as naphthalene and anthracene, although their spectra are recorded, no conclusions have been drawn with regard to structure nor has any theoretical work been reported. Similar remarks apply to complexes of nonalternant hydrocarbons such as azulene. Although innumerable complexes of olefins with various transition metals are known and admirably reviewed (84), no theoretical discussion of even a qualitative nature has been provided of their electronic spectra. A recent qualitative account of the electronic spectra of a series of cyclopentadienone, quinone, and thiophene dioxide complexes has been given by Schrauzer and Kratel (85). 

Cycl[3,2,2]azine (I) is related to annulenes as well as to nonalternant hydrocarbons 45 that is, it can be considered as an amino-substituted [10] annulene and at the same time as isoelectronic with the aceindenyl anion (41).46... 

SAD Spin-alternant determinant. The VB determinant with one electron per site and with alternating spins. Other terms describing the same determinant are the quasiclassical (QC) state, and the antiferromagnetic (AF) state. In nonalternant hydrocarbons, where compete spin alternation is impossible, the determinant is called MS AD, namely, the maximum spin-alternating determinant. The SAD MSAD are the leading terms in the wave function of molecules with one electron per site, for example, conjugated hydrocarbons. In radicals (e.g., allyl radical) the SAD is the root cause of spin polarization (i.e., negative spin densities flanked by positive ones). See Chapters 7 and 8. 

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