Carbocations dications

The propensity of S-S dications to undergo dealkylation was found to decrease in the order of methyl > ethyl > benzyl. This order of reactivity parallels the increase in the stability of the corresponding carbocations.94 Dealkylation of dication 77 affords thiosulfonium salt 78 in quantitative yield.95 Kinetic studies suggest SN1 mechanism of dealkylation. In addition, reaction of sulfoxide 79 with a substituent chiral at the a-carbon results in racemic amide 80 after hydrolysis. 

The results suggest that chinoid type structures are the predominant resonance contributors for 88. The IGLO/DZ//3-21G calculated 13C NMR chemical shifts of benzylic monocations 88 correlate reasonably well with the experimentally obtained data. The 13C NMR chemical shifts of the carbocation centers (CH2 carbon) are calculated 10.6-12.5 ppm too deshielded. Similar results were obtained for benzylic dications 89. NMR chemical shifts of arenium ions derived from various classes of polycyclic aromatic hydrocarbons have been calculated using GIAO-DFT methods.103... 

The possibility of trapping of the carbocation by a triflate anion followed by substitution of the triflate group by sulfide has also been suggested126, at least for the addition of bicyclic dithioether dications to alkenes and alkynes. 

Earlier progress in these studies has been summarized in reviews published in the last decade, emphasizing carbocations and oxidation dications, RCs, as well as reactive intermediates from the nitro- and nitroso-derivatives. The review article published in 1996 emphasized groundwork studies on protonation as well as oxidation (both RCs and stable dications) of polycyclic arenes and explored possible relationships between charge distribution and carcinogenicity, in concert with its... 

In contrast, a persistent carbocation could not be generated from 9,10-dihydro-BaP introduction of bulky substituents at C-6 prevented side reactions, and the initially formed carbocation underwent rearrangement to the corresponding bay-region carbocation. Introduction of methoxy substituents into the 1- or 3- positions of 9,10-dihydro-BaP-7(8//)-one increased its electrophilic reactivity to the extent that stable carboxonium-arenium dications were produced in FSO3H/SO2CIF (Fig. 9). 

The mono- and diprotonated carbocations and the two-electron oxidation dications derived from parent pyrene and its nonalternant isomers azupyrene (dicyclo-penta[e/, /]heptalene) (DCPH) 72 and dicyclohepta[eJ,g /z]pentalene (DCHP) 73 were studied at the B3LYP/6-31G(d) level (Fig. 29). The most likely site(s) for mono-and diprotonation were determined based on relative arenium ion energies and the structures of the energetically most favored carbocations were determined by... 

The prototypical pentacoordinated carbocation, the parent nonclassical carbocation, CH, 1, has been extensively studied in the gas phase as well as by theoretical calculations.Among the higher coordinate carbocations, the hexacoordinated methylium dication, 2, and heptacoordinated trication, 3, were also shown to be energy minima by ab initio calculations. High-level ab initio calculations show that they have C2V and Csv structures, respectively.Their isoelectronic boron analogs were also studied. 

The structure of the sandwiched bishomoaromatic dication was confirmed by theoretical calculations at the HF/6-31G level. The stabilization of the carbocation was shown to be mainly due to the bishomoaromatic interactions. The long-postulated longicyclic interactions do not contribute to the stability of the cation, as shown by the energies of the following isodesmic reactions... 

The dications display NMR spectra, which are very similar to those of allylic carbocations. The terminal carbons of the dienylic and the allylic systems of the carbodications 107 and 108 show between 192 and 198, characteristic of the typical allylic carbocations. The IGLO-calculated chemical shifts closely match with those of the experimentally observed values for these carbodications. 

In the 40 years since Olah s original publications, an impressive body of work has appeared studying carbocations under what are frequently termed stable ion conditions. Problems such as local overheating and polymerization that were encountered in some of the initial studies were eliminated by improvements introduced by Ahlberg and Ek and Saunders et al. In addition to the solution-phase studies in superacids, Myhre and Yannoni have been able to obtain NMR spectra of carbocations at very low temperatures (down to 5 K) in solid-state matrices of antimony pentafluoride. Sunko et al. employed a similar matrix deposition technique to obtain low-temperature IR spectra. It is probably fair to say that nowadays most common carbocations that one could imagine have been studied. The structures shown below are a hmited set of examples. Included are aromatically stabilized cations, vinyl cations, acylium ions, halonium ions, and dications. There is even a recent report of the very unstable phenyl cation (CellJ)... 

Long-lived cyclopropylcarbinyl cation chemistry, including spiro cations and dications, has been reviewed,7 and some of the more interesting newer carbocations, such as (1), are the subject of a short survey.8 The use of secondary deuterium isotope effects in the study of carbocation-forming reactions has been revisited,9 and the... 

If a carbocation or a dication at the same time is also a Hiickeloid An + 2)jt aromatic system, resonance can result in substantial stabilization. The simplest 2jt aromatic system is the Breslow s cyclopropenium ion 206.434 439 Recently, electronic and infrared spectra of the parent ion cyclo-C3H3+ (206, R = H) in neon matrices440 and the X-ray characterization of the tris(trimethylsilyl) derivative were reported.441 The destabilizing effect of the silyl groups was found to be significantly smaller than in vinyl cations. The ion was computed to be more stable than the parent cyclopropenium ion by 31.4 kcal mol1 [MP3(fc)/6-31 lG //6-31G +ZPVE level]. The alkynylcy-clopropenylium ions 207 have been reported recently.442... 

The aromatic nature of the presently discussed carbocations and dications have been further established by subjecting their NMR parameters to charge density chemical shift relationship449,475 77 originally developed by Spiesecke and Schneider.478,479 Furthermore, NICS (nucleus-independent chemical shift) developed by Schleyer et al.480 offers a simple and efficient probe for aromaticity. 

Isoprenoid acyclic polyene carbocations with 6, 14, and 18 tt-electrons were synthesized.138 Considering also previous data for carotenoid dications, an equation correlating /.max (ranging from 400 to 1100 nm) and the number of sp2 hybridized carbon atoms in the dication was developed. Dication (67) and an analogue with a different alkyl substitution pattern were prepared as PF6 salts.139 These dications form... 

Superelectrophilic onium dications have been the subject of extensive studies and their chemistry is discussed in chapters 4-7. Other multiply charged carbocationic species are shown in Table 2. These include Hogeveen s bridging, nonclassical dication (14)26 the pagodane dication (15)27 Schleyer s l,3-dehydro-5,7-adamantane dication (16)28 the bis(fluroenyl) dication (18)29 dications (17 and 19) 19a trications (20-21)19a,3° and tetracations (22-23).31 Despite the highly electrophilic character of these carbocations, they have been characterized as persistent ions in superacids. 

There have been two reports involving gitonic superelectrophiles composed of carboxonium ions and vinylic carbocations in a 1,3-relationship. In the reaction of 3-phenylpropynoic acid (65) with benzene in superacid the novel carboxonium-vinyl dication 66 is generated, followed by reaction with benzene and then cyclization (eq 22).26a Likewise, the unsaturated amide (67) gives the cyclization product in high yields (70-97%) in very strong acids (polyphosphoric acid, CF3SO3H, Nation SAC-13, or HUSY eq 23).30... 

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