Iodination molecular orbital calculation

In the atom-transfer reactions of iodine from aryl iodides to phenyl radical, intervention of [9-1-2] aryl(phenyl)-A3-iodanyl radicals is proposed [Eq. (86)] [3]. The ab initio molecular orbital study indicates that the diaryl-A3-iodanyl radicals are transition states in the atom-transfer reactions, but not intermediates [161]. Examples obtained by ab initio molecular orbital calculations with the B3LYP/6 - 31G(d) level are shown in Fig. 2. 

The spectrum of Cs Ij is complex, and three distinct iodine atoms with —2500, —1460, and —830 MHz can be assigned [94]. The highest value is attributed to the central atom in the Is" anion which is expected from previous molecular-orbital calculations to have hp close to unity. The complexes benzamide-HIs and amylose-Is give very similar spectra in which at least two different iodines can be discerned. This confirms that Ij" is present as part of the chromophore in amylose-Is, which is the familiar blue starch-iodine complex. A full analysis of the bonding was... 

PhI(OAc)2. As a result of the central oxygens, the electron-rich cavity of macrocycle 180 is suitable for complexation of metal cations. Specifically, ESI-MS data indicate that macrocycles 178-181 can selectively form complexes with sodium cations in the presence of K+, Li+, Ag+, or Pb + [241], The self-assembly of monomeric benziodazoles 177 into macrocyclic molecules 178-181 was studied using molecular orbital calculations [331]. The driving force for the self-assembly is the formation of secondary bonding interactions between molecules and a rearrangement of primary and secondary bonding around iodine to place the least electronegative substituent in the equatorial position for each iodine in the trimer. 

Quideau and coworkers presented DFT calculations of spiroheterocylic iodine(III) intermediates to validate their participation in the PhI(OAc)2-mediated spiroketalization of phenolic alcohols [206]. Molecular orbital computational studies of (arylsulfonylimino)iodoarenes (ArINS02Ar ) [185], benziodazol-3-ones [207] and a series of or//to-substituted chiral organoiodine(III) compounds [208] have been reported in the literature. Results of these calculations were found to be in good agreement with X-ray structural data for these compounds. 

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