Faculty


Rybak-Akimova

Elena V. Rybak-Akimova

Department of Chemistry
Pearson Chemistry Laboratory
62 Talbot Avenue
Tufts University 
Medford, MA 02155 

Office: P-310

Tel: 617-627-3413  Fax: 617-627-3443

E-mail: elena.rybak-akimova@tufts.edu 

Research Homepage


Current Appointment

 

Professor of Chemistry, Department of Chemistry

 

Education

 

Post-Doctoral 1993-97, University of Kansas
Ph. D., 1987, Pisarzhevsky Institute, Ukrainian Academy of Sciences
M. Sc., 1983, Shevchenko University, Ukraine

 

Research Interests


Inorganic Chemistry.  The main theme of Professor Rybak-Akimova's research is understanding the selectivity of small-molecule binding and activation with transition metal complexes in order to design highly specific reagents and catalysts. This research is significant to solving fundamental problems in enzyme mimicry and to meeting industrial demand. The group focuses on two bio-inspired approaches to the problem of selectivity in substrate binding and transformations: (1) introducing specific substrate binding sites onto transition metal platforms (design of molecular tweezers), and (2) investigating the mechanisms of small molecule activation at the metal centers and specific reactivities of transient metal containing intermediates formed in these processes. These principles are widely used by natural metalloenzymes and antibiotics. For example, bleomycin, a well known antibiotic and anticancer drug, binds to DNA and recruits iron to bind oxygen and to generate a highly reactive oxidant that mediates oxidative cleavage. This cleavage is believed to be responsible for biological activity of bleomycin.

 

Selected Recent Publications

 

“H2O2 activation with biomimetic non-haem iron complexes and AcOH: Connecting the g = 2.7 EPR signal with a visible chromophore,” O.V. Makhlynets, W.N. Oloo, Y.S. Moroz, I.G. Belaya, T.D. Palluccio, A.S. Filatov, P. Müller, M.A. Cranswick, L. Que, Jr., E.V. Rybak-Akimova. Chem. Commun.201450, 645-648.


“(2R,2’S—2,2’-Bipiperidine-1,1’-diium dibromide,” G. Yang, B.C. Noll, E.V. Rybak-Akimova. Acta Cryst. E.201369(11), o1711.

 

“Thermodynamic and kinetic study of cleavage of the N-O bond of N-oxides by a vanadium(III) complex: Enhanced oxygen atom transfer reaction rates for adducts of nitrous oxide and mesityl nitrile oxide,” T.D. Palluccio, E.V. Rybak-Akimova, S. Majumdar, X. Cai, M. Chui, M. Temprado, J.S. Silvia, A.F. Cozzolino, D. Tofan, A. Velian, C.C. Cummins, B. Captain, C.D. Hoff. J. Am. Chem. Soc.2013135, 11357-11372.

 

“Rationalization of the barrier height for the p-Z-styrene epoxidation by iron(IV)-oxo porphyrin cation radicals with variable axial ligands,” D. Kumar, R. Latifi, S. Kumar, E.V. Rybak-Akimova, M.A. Sainna, S.P. de Visser. Inorg. Chem.201352, 7968-7979.

 

“Characterization of metastable intermediates formed in the reaction between a Mn(II) complex and dioxygen, including a crystallographic structure of a binuclear Mn(III)-peroxo species,” M.K. Coggins, X. Sun, Y. Kwak, E.I. Solomon, E. Rybak-Akimova, J. A. Kovacs. J. Am. Chem. Soc.2013135, 5631-5640.

 

“Factors affecting the carboxylate shift upon formation of nonheme diiron-O2 adducts,” J. Frisch, R. McDonnell, E.V. Rybak-Akimova, L. Que, Jr. Inorg. Chem.201352, 2627-2636.

 

“Does hydrogen-bonding donation to manganese(IV)-oxo and iron(IV)-oxo oxidants affect the oxygen-atom transfer ability? A computational study” R. Latifi, M.A. Sainna, E.V. Rybak-Akimova, S.P. de Visser. Chem. Eur. J.201319, 4058-4068

 

“Kinetic insights into the reactivity of the intermediates generated from hydrogen peroxide and diiron(III) complex with tris(picolyl)amine (TPA),” X. Sun, S.V. Kryatov, E.V. Rybak-Akimova. Dalton Trans.201342, 4427-4435

 

“Two-step binding of O2 to vanadium(III) tris-anilide complex to form a non-vanadyl vanadium(V) peroxo complex,” A.F. Cozzolino, D. Tofan, C.C. Cummins, M. Temprado, T.D. Palluccio, E.V. Rybak-Akimova, S. Majumdar, X. Cai, B. Captain, C.D. Hoff. J. Am. Chem. Soc.2012134, 18249 -18252.


M.S. Kryatova, O.V. Makhlynets, A.Y. Nazarenko, E.V. Rybak-Akimova. Nickel(II) complexes with tetradentate N4 ligands: Synthesis, structure, electrochemistry, and thermochromism in solution. Inorg. Chim. Acta2012387, 74-80.


“Oxygen atom transfer mediated by an Fe(IV)/Fe(II) macrocyclic complex containing pyridine and tertiary amine donors,” W. Ye, R.J. Staples, E.V. Rybak-Akimova. J. Inorg. Biochem.2012115, 1-12.


“Role of Fe(IV)-oxo intermediates in stoichiometric and catalytic oxidations mediated by iron pyridine-azamacrocycles,” W. Ye, D.M. Ho, S. Friedle, T.D. Palluccio, E.V. Rybak-Akimova. Inorg. Chem., 201251, 5006-5021.

 

“New efficient iron catalyst for olefin epoxidation with hydrogen peroxide,” E.A. Mikhalyova, O.V.Makhlynets, T.D. Palluccio, A.S. Filatov, E.V. Rybak-Akimova. Chem. Commun.201248, 687-689.


“Mechanistic investigation of cyclohexane oxidation by a binuclear non-heme iron model complex: Evidence of product inhibition by low-temperature UV-vis stopped-flow spectroscopic kinetic studies,” L.C. Gregor, G.T. Rowe, E.V. Rybak-Akimova, J.P. Caradonna. Dalton Trans., 201241, 777-782.


“N1,N2, N3-Tris((2,6 dimethylphenyl)amino)ethyl)amine,” Y.S. Moroz, M.K. Takase, P. Müller, E.V. Rybak-Akimova. Acta Cryst. E201167(Pt 12), o3421.


“Bis (µ2-η2:η2-2,4,6-trimethylbenzonitrile) bis [(N-isopropyl-3,5-dimethylanilido)-molybdenum)](Mo—Mo),” Y.S. Moroz, A.F. Cozzolino, E.V. Rybak-Akimova, C.C. Cummins. Acta Cryst.2011, E67, m1643-m1644.


“Fast carbon dioxide fixation by 2,6-pyridinecarboxamidato-nickel(II)-hydroxide complexes: Influence of changes in reactive site environment on reaction rates,” D. Huang, O. V. Makhlynets, L.L. Tan, S.C. Lee, Elena V. Rybak-Akimova, R.H. Holm. Inorg. Chem.201150(20), 10070-10081.


"Mechanistic Studies of the O2-Dependent Aliphatic Carbon−Carbon Bond Cleavage Reaction of a Nickel Enolate Complex", L. M. Berreau, T. Borowski, K. Grubel, C. J. Allpress, J. P. Wikstrom, M. E. Germain, E. V. Rybak-Akimova, D. L. Tierney, Inorg. Chem., 2011, 50, 1047-1057.

 

"Oxygen Binding to [Pd(L)(L′)] (L=NHC, L′= NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex",  X. Cai, S.  Majumdar, G. C. Fortman, C. S. J. Cazin, A. M. Z. Slawin, C. Lhermitte, R. Prabhakar, M. E. Germain, T. Palluccio, S. P. Nolan, E. V. Rybak-Akimova, M. Temprado, B. Captain, C. D. Hoff, J. Am. Chem. Soc., 2011, 133, 1290-1293.

 

"Aromatic hydroxylation at a non-heme iron center: observed intermediates and insights into the nature of the active species", O. V. Makhlynets, E. V. Rybak-Akimova, Chem. Eur. J., 2010, 16, 13995-14006

 

"Steric and counterion effects on the structure of dipicolylamine nickel complexes", J. P. Wikstrom, A. S. Filatov, R. J. Staples, C. R. Guifarro and E. V. Rybak-Akimova, Inor. Chim. Acta., 2010, 363, 884-890.

 

"Carbonate formation within a nickel dimer: synthesis of a coordinatively unsaturated bis(mu-hydroxo) dinickel complex and its reactivity toward carbon dioxide", J. P. Wikstrom, A. S. Filatov, E. A. Mikhalyova, M. Shatruk, B. M. Foxman, and E. V. Rybak-Akimova, Dalton Trans., 2010, 39, 2504-14.

 

"Condensation of nitriles with amides promoted by coordinatively unsaturated bis-nickel(II)-hydroxy complex: a new route to alkyl- and aryl-imidoylamidines", J. P. Wikstrom, A. S. Filatov, E. V. Rybak-Akimova, Chem. Comm., 2010, 46, 424-426.

 

"Coordination-Mode Control of Bound Nitrile Radical Complex Reactivity: Intercepting End-on Nitrile-Mo(III) Radicals at Low Temperature", M. E. Germain, M. Temprado, A. Castonguay, O. P. Kryatova,  E. V. Rybak-Akimova, J. J. Curley, A. Mendiratta, Y-C. Tsai, C. C. Cummins, R. Prabhakar, J. E. McDonough, E. James, and C. D. Hoff, J. Am. Chem Soc., 2009, 131, 15412-15423.

 

"Nickel(II) Complexes of Monofunctionalized Pyridine-Azamacrocycles: Synthesis, Structures, Pendant Arm "On-Off" Coordination Equilibria, and Peroxidase-like Activity", V. G. Organo, A. S.  Filatov, S. Alexander, J. S. Quartararo, , Z. M. Friedman, and E. V. Rybak-Akimova, Inorg. Chem., 2009, 48, 8456-8468.

 

Complete listing of publications HERE