Density functional theory redox properties

AMI semi-empirical and B3LYP/6-31G(d)/AMl density functional theory (DFT) computational studies were performed with the purpose of determining which variously substituted 1,3,4-oxadiazoles would participate in Diels-Alder reactions as dienes and under what conditions. Also, bond orders for 1,3,4-oxadiazole and its 2,5-diacetyl, 2,5-dimethyl, 2,5-di(trifluoromethyl), and 2,5-di(methoxycarbonyl) derivatives were calculated <1998JMT153>. The AMI method was also used to evaluate the electronic properties of 2,5-bis[5-(4,5,6,7-tetrahydrobenzo[A thien-2-yl)thien-2-yl]-l,3,4-oxadiazole 8. The experimentally determined redox potentials were compared with the calculated highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) energies. The performance of the available parameters from AMI was verified with other semi-empirical calculations (PM3, MNDO) as well as by ab initio methods <1998CEJ2211>. 

J. VandeVondele, R. Lynden-Bell, E. J. Meijer, and M. Sprik (2006) Density functional theory study of tetrathiafulvalene and thianthrene in acetonitrile structure, dynamics and redox properties. J. Phys. Chem. B 110, p. 3614... 

In this review we focus on applications of the LFDFT method to complexes of 3d metals and compare these with both spectral data from well documented sources [1, 2] and other theoretical methods, such as the spectroscopically oriented Cl (SORCI) method [7] and time-dependent density-functional theory (TDDFT) [8-17]. In particular we intend to emphasize applications to systems with atypical electronic properties of interest for bio-inorganic chemistry and homogeneous catalysis. These systems include macrocyclic amines of Fe in various oxidation states, which are of interest for enzymatic and catalytic reactivity both for redox and bond-breaking reactions. 

Cu-ATSM is selectively trapped in highly reducing hypoxic tissue but not in less reducing normal tissue. On the other hand, Cu-PTSM is reduced in both normoxic and hypoxic tissue. Hypoxia selectivity has been correlated to the reduction potential of the molecule that is in turn related to the alkyl group substitution. The reduction potential of Cu-ATSM is about 100 mV lower than that of Cu-PTSM. Density Functional Theory and chemical reactivity studies attempt to correlate the structure and redox properties of bis(thiosemicarbazones) with the characteristics of the LUMOs (metal or ligand based) and chemical reactivity. The fast and selective uptake of jjj hypoxic... 

Austin JP, Sundararajan M, Vincent MA and Hillier IH 2009 The geometric structures, vibrational frequencies and redox properties of the actinyl coordination complexes ([ano2 (1) n] m an= u, pu, np 1= h2o, cl-, co32-, ch3co2-, oh-) in aqueous solution, studied by density functional theory methods. Dalton Transactions (30), 5902-5909. 

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