Intermediate delocalized

In cases of more effective 7t-electron donor or tz-donor neighboring groups, as is the case in forming /3-phenylethyl (studied by Don Cram from UCLA Nobel Prize in chemistry, 1987) or /3-halogen bridged species, these have sufficient electrons to form 2e-2c bonds (with some intermediate delocalization). 

The whole difference between the two mechanisms is the formulation of the structure of the intermediate The structures in the two versions of the mechanism for this reaction are only very subtly different. In one, the constituent structures are contributing resonance forms to a single intermediate delocalized species in the other they are equilibrating molecules, each with its own separate existence. 

Nonclassical ions, a term first used by John Roberts (an outstanding Caltech chemist and pioneer in the field), were defined by Paul Bartlett of Harvard as containing too few electrons to allow a pair for each bond i.e., they must contain delocalized (T-electrons. This is where the question stood in the early 1960s. The structure of the intermediate 2-norbornyl ion could only be suggested indirectly from rate (kinetic) data and observation of stereochemistry no direct observation or structural study was possible at the time. 

Section 11 14 Benzylic carbocations are intermediates in SnI reactions of benzylic halides and are stabilized by electron delocalization... 

One way to assess the relative stabilities of these various intermediates is to exam me electron delocalization m them using a resonance description The cyclohexadienyl cations leading to o and p mtrotoluene have tertiary carbocation character Each has a resonance form m which the positive charge resides on the carbon that bears the methyl group... 

C 1 IS more reactive because the intermediate formed by electrophilic attack there IS a relatively stable carbocation A benzene type pattern of bonds is retained m one nng and the positive charge is delocalized by allylic resonance... 

Reactions at the a-carbons have been of considerable kiterest because it is at these positions that enzymatic oxidation, which is beheved to initiate the events leading to carcinogenic metaboUtes, generally occurs (5,7,8,73). The a-hydrogens exchange readily as shown in the following where D represents H. This exchange apparentiy results from stabilization of an anionic intermediate by electron delocalization (74,75). 

Pyrrole has a planar, pentagonal (C2 ) stmcture and is aromatic in that it has a sextet of electrons. It is isoelectronic with the cyclopentadienyl anion. The TT-electrons are delocalized throughout the ring system, thus pyrrole is best characterized as a resonance hybrid, with contributing stmctures (1 5). These stmctures explain its lack of basicity (which is less than that of pyridine), its unexpectedly high acidity, and its pronounced aromatic character. The resonance energy which has been estimated at about 100 kj/mol (23.9 kcal/mol) is intermediate between that of furan and thiophene, or about two-thirds that of benzene (5). 

In aqueous alkaline conditions with chloroacetic acid the pyrido[4,3- f]pyrimidinethione (80) undergoes facile ring opening, attributed to the resonance stabilization of a delocalized covalent hydrate dianion intermediate (81) (82). Pyrido[2,3- f]pyrimidine-4-thiones (and... 

In general, five-membered heteroaromatic ring systems with one heteroatom all undergo preferential a rather than /3 electrophilic substitution. This is rationalized in terms of the more effective delocalization of charge in the intermediate (36) leading to a substitution than in the intermediate (37) leading to /3 substitution. 

Kinetic data on acetate displacement from C-3 using a number of sulfur and nitrogen nucleophiles in aqueous solution at near neutral pH demonstrate that the reaction proceeds by an 5 1 mechanism (B-72MI51004). The intermediate in this reaction is depicted as a dipolar allylic carbonium ion (9) with significant charge delocalization. Of particular significance in this regard is the observation that the free carboxylate at C-4 is required since... 

One of the structural implications of the delocalization of the negative charge, the identity of the two C—O bond lengths, intermediate between those of single and double bonds, has been verified by many crystal structure determinations. 

The electron-releasing methoxy group can interact directly to delocalize the charge and stabilize the intermediates leading to o- and p-bromomethoxybenzene. It cannot stabilize... 

The description of the nonclassical norbomyl cation developed by Wnstein implies that the nonclassical ion is stabilized, relative to a secondary ion, by C—C a bond delocalization. H. C. Brown of Purdue University put forward an alternative interpreta-tioiL He argued that all the available data were consistent with describing the intermediate as a rapidly equilibrating classical ion. The 1,2-shift that interconverts the two ions was presumed to be rapid relative to capture of the nucleophile. Such a rapid rearrangement would account for the isolation of racemic product, and Brown proposed that die rapid migration would lead to preferential approach of the nucleophile fiom the exo direction. 

In order for a substitution to occur, a n-complex must be formed. The term a-complex is used to describe an intermediate in which the carbon at the site of substitution is bonded to both the electrophile and the hydrogen that is displaced. As the term implies, a a bond is formed at the site of substitution. The intermediate is a cyclohexadienyl cation. Its fundamental structural characteristics can be described in simple MO terms. The a-complex is a four-7t-electron delocalized system that is electronically equivalent to a pentadienyl cation (Fig. 10.1). There is no longer cyclic conjugation. The LUMO has nodes at C-2 and C-4 of the pentadienyl structure, and these positions correspond to the positions meta to the site of substitution on the aromatic ring. As a result, the positive chargex)f the cation is located at the positions ortho and para to the site of substitution. 

The position selectivity for electrophilic substitution in the simple five-membered heteroaromatic rings is usually 2 > 3. This reflects the more favorable conjugation in intermediate A than in intermediate B. In structure A the remaining C=C bond can delocalize the positive charge more effectively than in B. Substituents on the ring can easily override this directive influence, however. 

The stabilizing role of other functional groups can also be described in resonance terms. Both electron-attracting groups such as carbonyl and cyano and electron-donating groups such as methoxy and dimethylamino have a stabilizing etfect on a radical intermediate at an adjacent carbon. The resonance structures which depict these interactions indicate delocalization of the unpaired electron onto the adjacent substituents ... 

The same mixture of H and I was obtained starting with either of the geometrically isomeric radical precursors E or F. A possible explanation is based on the assumption of a common radical conformer G, stabilized in the geometry shown by electron delocalization involving the radicaloid p-orbital, the p-peroxy oxygen and Jt of the diene unit. The structure of the compounds H and I were determined by H NMR spectra and the conversion of H to diol J, a known intermediate for the synthesis of prostaglandins. 

The difference between the two extremes is essentially that, in the former, the Re retains its valence electrons in its d orbitals whereas in the latter it loses 6 of them to delocalized ligand orbitals. In either case paramagnetism is anticipated since rhenium has an odd number of valence electrons. The magnetic moment of 1.79 BM corresponding to 1 unpaired electron, and esr evidence showing that this electron is situated predominantly on the ligands, indicates that an intermediate oxidation state is involved... 

Monochalcogenides, LnZ (Z = S, Se, Te), have been prepared for all the lanthanides except Pm, mostly by direct combination.They are almost black and, like the monoxides, have the NaCl structure. However, with the exceptions of SmZ, EuZ, YbZ, TmSe and TmTe, they have metallic conductivity and evidently consist of Ln -t- Z ions with 1 electron from each cation delocalized in a conduction band. EuZ and YbZ, by contrast, are semiconductors or insulators with genuinely divalent cations, but SmZ seem to be intermediate and may involve the equilibrium ... 

One possible explanation is that adamantyl cation, an intermediate in the reaction, is particularly unstable because it cannot accomodate a planar carbocation center (see Chapter 1, Problem 9). Examine the geometry of adamantyl cation. Does it incorporate a planar carbocation center Compare electrostatic potential maps of adamantyl cation and 2-methyl-2-propyl cation. Which cation better delocalizes the positive charge Assuming that the more delocalized cation is also the more stable cation, would you expect adamantyl tosylate to react slower or faster than tcrf-butyl tosylate Calculate the energy of the reaction. 

The first step in the addition of an electrophile such as HBr to an alkyne involves protonation and subsequent formation of an intermediate vinyl cation. Where does propyne protonate Compare energies of 1-methylvinyl and 2-methylvinyl cations. Which is more stable Why Measure CC bond distance in the more stable cation. Does the cation incorporate a full triple bond (as in propyne) or a double bond (as in propene). Examine atomic charges and electrostatic potential maps to locate the positive charge in the two cations. Is the more stable ion the one in which the charge is better delocalized Use the charges together with information about the ions geometry to draw Lewis structures (or a series of Lewis structures) for 1-methylvinyl and 2-methylvinyl cations. 

Another way to assess thiophene s reactivity is to compare the intermediate ions formed by addition of N02. Examine the structures, charge distributions and electrostatic potential maps of thiophene+nitronium at C2 and thiophene+nitronium at C3. Draw all of the resonance contributors needed to describe these structures. Which, if either, better delocalizes the positive charge Compare the energies of the two intermediates. Which product should form preferentially if the reaction is under kinetic control Are these results consistent with FMO theory ... 

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