This proposal has two main foci: the chemistry of iron porphyrins and the nature of chemical bonding to the proton (H+). The broad objective is to uncover new fundamental chemical knowledge that provides the basis for a molecular level understanding of hemoproteins and protons in chemical and biological systems. Specific objectives in metalloporphyrin research include: (i) the further development of a magnetochemical alternative to the familiar Spectrochemical Series, (ii) testing the applicability of the magnetochemical concept in a series of met-myoglobin derivatives, (iii) revisiting the concept of quantum mechanically admixed S = 3/2,5/2 spin states in iron(Ill) porphyrins, (iv) preparing an osmium porphyrin complex with xenon as a ligand, and (v) isolating """"""""sitting-atop"""""""" metalloporphyrin complexes -- reaction intermediates in the insertion of metal ions into free-base porphyrins. In research on the proton, intermediates in proton transfer and acid catalyzed reaction chemistry will be investigated. Specific objectives include (i) measuring the acid strength of carborane-based acids, (ii) investigating a new class of short, strong, low-barrier (SSLB) H-bonds (iii) isolating carbocations as carborane salts, (iv) investigating the fundamental chemistry of the hydronium ion (H30+) in water-deficient environments as models for enzyme active sites and membrane channels and (v) developing the chemistry of a new, strong, methylating reagent. Emphasis in these studies is placed on the definitive characterization of analytically pure materials by X-ray crystallography, a variety of spectroscopic methods (NMR, IR, electronic spectroscopy including NIR, Mossbauer, resonance Raman, etc.) and theory. Fundamental chemistry is the hidden engine of biomedical science. There are potential applications of carborane acids in steroidal metabolism disorders and MALDI protein analysis.
| 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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