The long term goal of this project is to understand the molecular chemistry of multicenter metalloproteins, particularly cytochrome oxidase and related hemoproteins, and to uncover fundamental new chemical phenomena related to such systems. A synthetic model compound approach is taken which emphasizes the definitive characterization of binucleating porphyrins which hold two metals in close proximity. Iron porphyrins with chelated copper will serve as cytochrome oxidase models; a more diverse selection of metals will allow an exploration of new structural and chemical reactivity aspects that are unique to binuclear systems. Particular emphasis will be placed on understanding spin-coupling phenomena in paramagnetic metal/metal and metal/ligand radical systems. The investigative techniques of single crystal X-ray structure determination and variable temperature magnetic susceptibility will be emphasized along with a variety of spectroscopic techniques (IR, UV-VIS Mossbauer, EPR, etc.). A detailed molecular level understanding of hemoproteins and related metalloproteins is based on fundamental chemical principles and must underlie medical approaches to the therapy of metalloprotein disorders (thalassemias, sickle cell anemia, etc.).
| Nava, Matthew; Stoyanova, Irina V; Cummings, Steven et al. (2014) The strongest Brønsted acid: protonation of alkanes by H(CHB(11)F(11)) at room temperature. Angew Chem Int Ed Engl 53:1131-4 |
| Reed, Christopher A; Stoyanov, Evgenii S; Tham, Fook S (2013) Hydrogen bonding versus hyperconjugation in condensed-phase carbocations. Org Biomol Chem 11:3797-802 |
| Reed, Christopher A (2013) Myths about the proton. The nature of H+ in condensed media. Acc Chem Res 46:2567-75 |
| Stoyanov, Evgenii S; Stoyanova, Irina V; Tham, Fook S et al. (2012) Evidence for C-H hydrogen bonding in salts of tert-butyl cation. Angew Chem Int Ed Engl 51:9149-51 |
| Stoyanov, Evgenii S; Gunbas, Gorkem; Hafezi, Nema et al. (2012) The R3O+···H+ hydrogen bond: toward a tetracoordinate oxadionium(2+) ion. J Am Chem Soc 134:707-14 |
| Nava, Matthew; Reed, Christopher A (2011) Triethylsilyl Perfluoro-Tetraphenylborate, [Et(3)Si][F(20)-BPh(4)], a widely used Non-Existent Compound. Organometallics 30:4798-4800 |
| Nava, Matthew J; Reed, Christopher A (2010) High yield C-derivatization of weakly coordinating carborane anions. Inorg Chem 49:4726-8 |
| Stoyanov, Evgenii S; Stoyanova, Irina V; Reed, Christopher A (2010) The structure of the hydrogen ion (H(aq)+) in water. J Am Chem Soc 132:1484-5 |
| Reed, Christopher A (2010) H(+), CH(3)(+), and R(3)Si(+) carborane reagents: when triflates fail. Acc Chem Res 43:121-8 |
| Stoyanov, Evgenii S; Stoyanova, Irina V; Tham, Fook S et al. (2009) H(aq)+ structures in proton wires inside nanotubes. J Am Chem Soc 131:17540-1 |
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