Synthesis and structure of novel perfluorinated iodinanes

Montanari, Vittorio; Desmarteau, D. D.; Pennington, William T.

doi:10.1016/s0022-2860(00)00502-0

Cited by 44 publications

(32 citation statements)

References 32 publications

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“…The calculated equilib rium geometric parameters and electronic characteristics of the singlet state of the I 3 + ion are listed in Table 1. It should be noted that the structure of the I 3 + ion is similar to the T shaped configurations of polyvalent iodine(III) derivatives RIX 2 (bond angle X-I-X is about 90-100°) 24 and the complexes I 3 + AlCl 4 -and I 3 + AsF 6 -(bond angles I-I-I are 101-104°). 23 The calculated thermodynamic characteristics of the reactions of formation of I 3 + cation (see Eqs (49)-(69)) are listed in Table 2.…”

Section: Methodsmentioning

confidence: 68%

“…The results obtained clearly show that generation of this cation from molecular iodine and I + ion (see Eq. (49)) is thermodynamically favorable and that the proportion of the decomposition channel of the protonated forms RXIH + to I 3 + is much higher than the decomposition to monocation I + in acid media or the decomposition to iodine radical upon homolysis of X-I bonds (cf., for instance, Eqs (1), (3) and (51); Eqs (7), (9) and (55); Eqs (22), (24) and (57); Eqs (10), (12) and (61); Eqs (13), (15) and (63); and Eqs (16), (18) and (65)). Moreover, calculations predict almost complete de composition of protonated iodine chloride ClH + I (see Eq.…”

Section: Methodsmentioning

confidence: 99%

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Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study

et al. 2006

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The electronic and spatial structures of a broad spectrum of neutral compounds with X-Hal (X = N, O, Cl; Hal = Cl, Br, I) bonds and their protonated forms and of differ ent electronic states of triiodide cation, I 3 + , were determined from density functional B3LYP/6 311G* quantum chemical calculations. The effects of the structure of these com pounds on the parameters of electrophilic reactivity were revealed and the thermochemical characteristics of homolytic and heterolytic X-Hal bond dissociation and of iodine transfer in hydroxyl containing solvents were calculated. Due to low homolytic bond dissociation ener gies of X-I, the formation of molecular iodine and triiodide cation I 3 + becomes thermody namically favorable and the cation should act as iodinating agent alternative to acylhypoiodites and N iodoimides. The solvation effects of MeOH and CH 2 Cl 2 on the X-Hal bond homolysis and heterolysis were determined using the PCM model.

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Section: Methodsmentioning

confidence: 68%

Section: Methodsmentioning

confidence: 99%

Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study

et al. 2006

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“…In this chapter only trends observed for prototypes of perfluoroalkyl and perfluoroaryl derivatives are presented. Structural data for some polyfluoroalkyliodine(III) compounds are reported by Pennington and coworkers[131]. Besides molecular parameters we discuss also intermolecular interactions.…”

mentioning

confidence: 88%

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

Frohn

Hirschberg

Wenda

et al. 2008

Journal of Fluorine Chemistry

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“…Our calculations gave a value of 103.3° for I 3 + , and the corresponding angles in I 3 + HSO 4 − and I 3 + CF 3 SO 3 − were estimated at 96.1 and 96.6°, respectively. These values are typical of multivalent iodine compounds [11] and complexes like I 3 + AlCl 4 − and I 3 + AsF 6 − [12]. The lowest unoccupied molecular orbital in the examined species is localized on the I-I-I fragment; this means that their electrophilicity is related mainly to central iodine atom.…”

Section: Evaluation Of the Reactivity And Regioselectivitymentioning

confidence: 76%

Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

2009

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Iodination of o-nitrotoluene in H 2 SO 4 or CF 3 SO 3 H at 0°C with compounds having a nitrogeniodine bond leads to the formation of isomeric mono-and diiodo derivatives whose ratio differs from the statistical value. The reaction of nitrobenzene with 2 equiv of N-I reagents in trifluoromethanesulfonic acid at 0°C takes less than 1 min and yields 79-85% of m-iodonitrobenzene. The electrophilic reactivity of the iodinating agents was estimated by quantum-chemical methods.The rate of electrophilic substitution reactions in the aromatic series and isomeric composition of the products are largely determined by the electrophile nature. In keeping with the Brown selectivity relationship, stronger electrophiles exhibit lower intramolecular selectivity in substitution reactions in the benzene ring [1]. The most reactive electrophiles give rise to a mixture of regioisomers whose ratio approaches statistical value. In the iodination with common iodinating systems, the reactivity and selectivity may be evaluated using the reaction with toluene as an example [2]. However, the procedure based on determination of the ratio of o-and p-iodotoluenes cannot be applied to reactions with superelectrophilic iodinating systems [3][4][5][6], which lead to the formation of a mixture of polyiodotoluenes containing mostly tri-and tetraiodo derivatives. Therefore, to estimate the selectivity of superelectrophilic iodinating systems we compared the compositions of products formed in the iodination of o-nitrotoluene (I) with reagents generated by dissolution of 1,3,4,6-tetraiodoglycoluril (TIG), 1,3-diiodo-5,5-dimethylhydantoin (DIH), and N-iodosuccinimide (NIS) in sulfuric acid [3, 5, 6] (Scheme 1).Traditional methods for the determination of the reactivity and regioselectivity of iodinating systems by analysis of the iodination products of nitroarene I cannot be used, for nitrotoluenes do not undergo iodination by common methods at 0°C. Detailed GC-MS study on the products of reactions of compound I with TIG-H 2 SO 4 , DIH-H 2 SO 4 , and NIS-H 2 SO 4 showed ( Table 1) that the use of stoichiometric amounts of the reagents (calculated on the active iodine) does not ensure complete conversion of I (Table 1, run nos. 1-3), and 30-35% of the initial compound remains unchanged.A similar conversion of other substrates at the same reagent-to-substrate ratio was noted by us previously [3][4][5][6]. Approximately similar selectivities were observed in the iodination with TIG-H 2 SO 4 and DIH-H 2 SO 4 . In the reaction with N-iodosuccinimide, the fraction of 4-iodo-2-nitrotoluene (II) was slightly larger than the fraction of 6-iodo-2-nitrotoluene (III), but the substrate conversion was lower.The reactions in the presence of 2 equiv of the iodinating agents (Table 1, run nos. 4-6) are characterized by appreciably reduced para-selectivity. However,

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Synthesis and structure of novel perfluorinated iodinanes

Cited by 44 publications

References 32 publications

Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study

Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study

Polyvalent perfluoroorgano- and selected polyfluoroorgano-halogen(III and V) compounds

Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

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