bond angle.pdfVIP

Rearrangements in Model Peptide-Type Radicals via Intramolecular Hydrogen-Atom Transfer by Damian Moran*a)b), Rebecca Jacobc), Geoffrey P. F. Wooda)b), Michelle L. Cooteb)c), Michael J. Daviesb)d), Richard A. J. O!Hairb)e), Christopher J. Eastonb)c), and Leo Radom*a)b)c) a) School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia (e-mail: dmoran@chem.usyd.edu.au; radom@chem.usyd.edu.au) b) ARC Centre of Excellence in Free Radical Chemistry and Biotechnology c) Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia d) Heart Research Institute, Camperdown, NSW 2050, Australia e) School of Chemistry, Bio21 Institute, University of Melbourne, Victoria 3010, Australia In fond memory of our friend and colleague, Professor Hanns Fischer, and in recognition of his distin- guished contributions to chemistry Intramolecular H-atom transfer in model peptide-type radicals was investigated with high-level quantum-chemistry calculations. Examination of 1,2-, 1,3-, 1,5-, and 1,6[C$ N]-H shifts, 1,4- and 1,7[C$ C]-H shifts, and 1,4[N$ N]-H shifts (Scheme 1), was carried out with a number of theoretical methods. In the first place, the performance of UB3-LYP (with the 6-31G(d), 6-31G(2df,p), and 6- 311+G(d,p) basis sets) and UMP2 (with the 6-31G(d) basis set) was assessed for the determination of radical geometries. We found that there is only a small basis-set dependence for the UB3-LYP structures, and geometries optimized with UB3-LYP/6-31G(d) are generally sufficient for use in conjunction with high-level composite methods in the determination of improved H-transfer thermochemistry. Methods assessed in this regard include the high-level composite methods, G3(MP2)-RAD, CBS-QB3, and G3//B3-LYP, as well as the density-functional methods B3-LYP, MPWB1K, and BMK in association with the 6-31+G(d,p) and 6-311++G(3df,3pd) basis sets. The high-level methods give results that are close to one another, while the recently developed functional