Ding, F.; Harman, D. Stereoselective Tandem 1,4-Addition Reactions for Benzenes: A Comparison of Os(II), Re(I), and W(0) Systems. Journal of the American Chemical Society 2004, 126, 13752-13756.
Publications
2004
2003
Trindle, C.; Sacks, G.; Harman, D. Computational Modeling of Complexes of Penta-Ammine Osmium (II) with Aromatic Ligands. International Journal of Quantum Chemistry 2003, 92, 457-456.
Abstract Complexation of aromatic species with penta-ammine osmlium (II)[Os]has remarkable effects on their structure and reactivity. The η2-complexed dearomatized ligand can be encouraged to react in ways of great convenience in synthetic projects. We model the structure of complexes of [Os] with various descriptions of correlation and in various bases. The most satisfactory method for structures is a perturbation correlation corrected model (MP2) with a hybrid basis, 6-31G* on all but osmium, and the LANL2DZ basis and associated pseudopotential for that heavy atom. A B3LYP/hybrid scheme seems to produce better estimates of binding and isomerization energies for a range of ligands, including hydrocarbons, heteroaromatics, and substituted benzenes. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003
Stokes, S. M.; Ding, F.; Smith, P. L.; Keane, J. M.; Kopach, M. E.; Jervis, R.; Sabat, M.; Harman, D. Formation of o-Quinone Methides from η2-Coordinated Phenols and Their Controlled Release from a Transition Metal To Generate Chromans. Organometallics 2003, 22, 4170-4171.
Smith, K. S.; Smith, P. L.; Heady, T. N.; Trugman, J. M.; Harman, D.; Macdonald, T. L. In Vitro Metabolism of Tolcapone to Reactive Intermediates: Relevance to Tolcapone Liver Toxicity. Chemical Research in Toxicology 2003, 16, 123-128.
Schiffler, M. A.; Friedman, L. A.; Brooks, B. C.; Sabat, M.; Harman, D. Stereoselective Aldehyde Addition to Rhenium-Coordinated Furans. Organometallics 2003, 22, 4966-4972.
Meiere, S. H.; Keane, J. M.; Gunnoe, B.; Sabat, M.; Harman, D. Binding and Activation of Aromatic Molecules by a Molybdenum π-Base. Journal of the American Chemical Society 2003, 125, 2024-2025.
Graham, P. M.; Meiere, S. H.; Sabat, M.; Harman, D. Dearomatization of Benzene, Deamidization of N,N-Dimethylformamide, and a Versatile New Tungsten π Base. Organometallics 2003, 22, 4364-4366.
Friedman, L. A.; You, F.; Sabat, M.; Harman, D. Rhenium-Promoted Diastereo- and Enantioselective Cyclopentannulation Reactions: Furans as 1,3-Propene Dipoles. Journal of the American Chemical Society 2003, 125, 14980-14981.
Bergman, R. G.; Cundari, T. R.; Gillespie, A. M.; Gunnoe, B.; Harman, D.; Klinckman, T. R.; Temple, D.; White, D. P. Computational Study of Methane Activation by TpRe(CO)2 and CpRe(CO)2 with a Stereoelectronic Comparison of Cyclopentadienyl and Scorpionate Ligands. Organometallics 2003, 22, 2331-2337.
2002
Valahovic, M. T.; Keane, J. M.; Harman, D. Osmium-and Rhenium-Mediated Dearomatization Reactions with Arenes. Modern Arene Chemistry 2002, 297–329.
The fragments fOs(NH 3 ) 5g2þ and fTpRe(CO)(L)g (where L ¼ 1-methylimidazole, pyridine,
PMe3 , or tert-butylisonitrile) form stable h2 -coordinate complexes with a wide variety of are-
nes. The act of coordination greatly reduces the aromatic character of these ligands and, as a
consequence, activates them towards various organic reactions. In particular, the addition of
carbon-based electrophiles to arenes is notably enhanced relative to the free aromatic mole-
cules. The resulting arenium intermediates are stabilized by metal backbonding to the point
that they may be isolated and subsequently subjected to a variety of carbon-based nucleo-
philes. The overall vicinal difunctionalization of two ring carbons may be accomplished with
excellent stereo- and regiocontrol.