hypervalent iodine

Hypervalent iodine derivatives with aryl substituents (1-4) represent a unique class of cross-conjugated materials for which little has been revealed about their electronic and structural properties. Iodonium salts with thiophene and bithiophene substituents can readily be assembled, and they provide us with a group of molecules that possess interesting and potentially useful optical properties. The structural and optical properties of these compounds as a function of their structure are characterized using X-ray crystallographic analysis, UV/Vis spectroscopy, and the nonlinear optical Z-scan technique.[1-2]

We also have a long standing interest in the solid state structure and synthetic usefulness of interesting hypervalent iodine reagents. Iodonium salts show a remarkable level of secondary bonding interactions in the solid state, and these interactions govern many aspects of their chemistry, including solubility and reactivity. Examples under study include chiral I(III) based macrocyclic assemblies as shown in Figure 1, and chiral I(V) oxidants, such as the one shown in Figure 2.[3-5]

Figure 1. Macrocyclic self-assembly of an amino acid derived benziodazole.

Figure 2. X-ray crystal structure of a chiral Iodine(V) oxidant.

Recent papers:

[1] "Thienyl(phenyl)iodonium Triflates – Structural and Linear and Nonlinear Optical Behavior of Hypervalent Iodine Derivatives," R. R. Tykwinski, K. Kamada, D. Bykowski, K. Ohta, R. McDonald Adv. Mater. 2000, 12, 133-137.

[2] "Structural and Electronic Characteristics of Thienyl(aryl)iodonium Triflates," D. Bykowski, R. McDonald, R.J. Hinkle, R.R. Tykwinski, J. Org. Chem. 2002, 67, 2798–2804.

[3] "Preparation and Reductive Decomposition of 2-Iodoxybenzenesulfonic Acid; X-Ray Crystal Structure of 1H-1-Hydroxy-1,2,3-benziodoxathiole 3,3-dioxide," A.Y. Koposov, D.N. Litvinov, V.V. Zhdankin, R. McDonald, R.R. Tykwinski, Eur. J. Org. Chem. 2006, 4791-4795.

[4] "Esters of 2-Iodoxybenzoic Acid (IBX-Esters): Hypervalent Iodine Oxidizing Reagents with a Pseudobenziodoxole Structure," V.V. Zhdankin, A.Y. Koposov, D.N. Litvinov M.J. Ferguson, R. McDonald, T. Luu, R.R. Tykwinski, J. Org. Chem. 2005, 70, 6484-6491.

[5] "IBX Amides: A New Family of Hypervalent Iodine Reagents," V.V. Zhdankin, A.Y. Koposov, B.C. Netzel, Nikolai V. Yashin, M.J. Ferguson, B.P. Rempel, R.R. Tykwinski, Angew. Chem. Int. Ed. 2003, 42, 2194-2196.

[6] "Esters of 2-Iodoxybenzoic Acid: Soluble and Stable Periodinane Oxidizing Reagents,” V.V. Zhdankin, D.N. Litvinov, A.Y. Koposov, T. Luu, M.J. Ferguson, R. McDonald, R.R. Tykwinski, ChemComm 2003, 106-107.

[7] "Preparation, Structure, and Unexpected Chemistry of Phosphoranyl Derived Benziodoxoles," V. V. Zhdankin, O. Maydanovych, J. Herschbach, R. McDonald, R. R. Tykwinski, J. Am. Chem. Soc. 2002, 124, 11614–11615.

[8] "Secondary Bonding–Directed Self–Assembly of Amino Acid Derived Benziodazoles: Synthesis and Structure of Novel Hypervalent Iodine Macrocycles," V.V. Zhdankin, A.E. Koposov, J.T. Smart, R.R. Tykwinski, R. McDonald, A. Morales–Izquierdo, J. Am. Chem. Soc. 2001, 123, 4095–4096.

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