Hypervalent iodine compounds structure

The structure and reactivity of several specific classes of hypervalent iodine compounds have been investigated theoretically. Varvoglis, Tsipis and coauthors have studied the geometry and electronic stmcture of some hypervalent iodine compounds PhIX2 by means of extended Hlickel and CNDO/2 quantum chemical approaches [200], The bonding was analyzed in terms of both the model of delocalized MOs on the basis of interactions between fragment MOs derived from EHMO-SCCC calculations and that of localized MOs derived by the CNDO/2 method. The ability of these compounds to afford c -addition products with alkenes via a synchronous molecular addition mechanism was found to be theoretically feasible [200]. 

Aziridines are key structural motifs present in natural products such as mitomycins and azinomycins and versatile building blocks which can undergo various useful transformations. Hypervalent iodine-mediated intramolecular aziridinations of allylic carbamates and reaction of A-tosyliminophenyliodinane (Phi = NTs) with double bonds have been reported to be efficient and practical routes to access these three-membered rings. Allylic carbamates 71 undergo enantioselective aziridine formation on oxidation with chiral binaphthyl hypervalent iodine compound 72 (Scheme 28) [86]. 

In these latter compounds, the hypervalent iodine may be associated with oxyanions such as perchlorate, trifluoroacetate, and triflate, as verified by the crystal structure of the trifluoroacetate derivative (41). It seems likely that the mode of binding of... 

Hypervalent Iodine Chemistry Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds, First Edition. Viktor V. Zhdankin. 2014 John Wiley Sons, Ltd. Published 2014 by John Wiley Sons, Ltd. 

The structural aspects of polyvalent iodine compounds were previously summarized in several books and reviews [20, 30, 32, 127]. In general, the molecular structure of and -iodanes is predetermined by the nature of hypervalent bonding discussed in Section 1.3. The key stmctural features of the hypervalent organoiodine compounds available from numerous X-ray data may be summarized as follows ... 

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