CHEMICAL AND BIOLOGICAL SCIENCES CHEMICAL AND BIOLOGICAL SCIENCES
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Andreja Bakac Senior Scientist 29 Spedding Hall
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PERSONAL HISTORY
RESEARCH INTERESTS
Kinetics and mechanisms of inorganic and organometallic reactions; catalytic oxidation with molecular oxygen; activation of dioxygen by transition metal complexes; chemistry of reactive intermediates in transition metal-dioxygen interactions; solution chemistry of free radicals; use of laser-flash photolysis and other photochemical methods to generate and observe organic and inorganic transients, including free radicals, intermediates in dioxygen activation, high-valent metal complexes, and excited electronic states.
RECENT PUBLICATIONS
M. J. Vasbinder and A. Bakac, "Kinetics and Mechanism of the Reactions of Ozone with Superoxo, Hydroperoxo, and Hydrido Complexes of Rhodium(III)", Inorg. Chim. Acta, submitted.
O. Pestovsky and A. Bakac, "Identification and Characterization of Aqueous Ferryl(IV) Ion", ACS Symposium Series, accepted.
E. Szajna-Fuller and A. Bakac, "Thermodynamics of Oxygen Activation by Macrocyclic Complexes or Rhodium", Inorg. Chem., accepted.
M. Furczon, O. Pestovsky, and A. Bakac, "Kinetics of Dissociation of Molecular Oxygen from a Superoxorhodium Complex, and Reactivity of a Macrocyclic Rhodium(II) Ion",
Inorg. Chem., accepted.
M. Cheng and A. Bakac, "Kinetics and Mechanism of the Reaction of Cr(II) Aqua Ions with Benzoylpyridine N-oxide", Dalton Transactions 2007, 2077-2082.
M. J. Vasbinder and A. Bakac, "Hydrogen Atom Transfer From Transition Metal Hydroperoxides, Hydrogen Peroxide, and Alkyl Hydroperoxides to Superoxo and Oxo Metal Complexes", Inorg. Chem. 2007, 46, 2921-2928.
M. J. Vasbinder and A. Bakac, "Kinetics of Oxidation of Nitroxyl Radicals with Superoxometal Complexes of Chromium and Rhodium", Inorg. Chem. 2007, 46, 2322-2327.
M. Kotowski, R. Marcec, V. Butkovic, A. Bakac, and M. Orhanovic, "Preparation and Characterization of Pyridine N-Oxide Complexes of Chromium(III)", Eur. J. Inorg. Chem. 2006, 2894-2899.
A. Bakac, "Aqueous Chemistry of Rhodium(III) Hydrides and of Monomeric Rhodium(II) Complexes", Dalton Transactions 2006, 1589-1597.
A. Bakac, "Kinetic And Mechanistic Studies of The Reactions of Transition Metal-Activated Oxygen With Inorganic Substrates", Coord. Chem. Rev. 2006, 250, 2046-2058.
K. Lemma, A. Ellern and A. Bakac, "Ligand Effect on the Kinetics of Hydroperoxochromium(III) - Oxochromium(V) Transformation and the Lifetime of Chromium(V)", Dalton Transactions 2006, 58-63.
O. Pestovsky and A. Bakac, "Aqueous Ferryl(IV) Ion. Kinetics of Oxygen Atom Transfer to Substrates, and Oxo Exchange with Solvent Water" Inorg. Chem. 2006, 45, 814-820.
O. Pestovsky and A. Bakac, "Competing Coordination and Oxygen Atom Transfer in a Reaction Between Triarylphosphines and a Chromium Hydroperoxo Complex", Inorg. React. Mech. 2005, 5, 245-254.
O. Pestovsky, S. Stoian, E. L. Bominaar, X. Shan, E. Münck, L. Que, Jr., and A. Bakac, "Aqueous FeIV=O: Spectroscopic Identification and Oxo Group Exchange" Angew. Chem., Int. Ed. 2005, 44, 6871-6874.
M. Hung and A. Bakac, "Kinetics and Mechanism of Acid-Catalyzed Oxidation of Bromide Ions by Aqueous Chromyl(IV) Complex", Inorg. Chem. 2005, 44, 9293-9298.
J. A. Nieweg, K. Lemma, B. G. Trewyn, V. S.-Y. Lin, and A. Bakac, "Mesoporous Silica-Supported Uranyl: Synthesis and Photoreactivity", Inorg. Chem. 2005, 44, 5641-5648.
O. Pestovsky and A. Bakac, "Oxygen Activation by a Macrocyclic Chromium Complex. Mechanism of Hydroperoxo-Chromium(III) to Oxo-Chromium(V) Transformation", Dalton Trans. 2005, 556-560.
O. Pestovsky and A. Bakac, "Reactivity of Aqueous Fe(IV) in Hydride and Hydrogen Atom Transfer Reactions", J. Am. Chem. Soc. 2004, 126, 13757-13764.
K. Lemma and A. Bakac, "Kinetics of Acid-Catalyzed O-atom Transfer from a Hydroperoxorhodium Complex to Organic and Inorganic Substrates", Inorg. Chem. 2004, 43, 6224-6227.
A. Bakac, C. Shi, and O. Pestovsky, "Acid-Catalyzed Oxidation of Iodide Ions by Superoxometal Complexes of Rhodium and Chromium", Inorg. Chem. 2004, 43, 5416-5421.
K. Lemma and A. Bakac, "Reduction and Oxidation of Hydroperoxo Rhodium(III) Complexes by Halides and Hypobromous Acid", Inorg. Chem. 2004, 43, 4505-4510.
A. Bakac, "Dioxygen Activation by Transition Metal Complexes. Atom Transfer and Free Radical Chemistry in Aqueous Media", Adv. Inorg. Chem. 2004, 55, 1-59.
O. Pestovsky and A. Bakac, "Direct Kinetic Studies of Atom Transfer and Electron Transfer Reactions of Hydroperoxo and High-Valent Oxo Complexes of Chromium", J. Am. Chem. Soc. 2003, 125, 14714-14715.
K. Lemma, A. Ellern and A. Bakac, "1H NMR Studies of Ligand and H/D Exchange Reactions of cis- and trans- ([14]aneN4)(H2O)RhH2+ in Aqueous Solutions", Inorg. Chem. 2003, 42, 3662-3669.
O. Pestovsky and A. Bakac, "Superoxometal-Catalyzed Co-oxidation of Alcohols and Nitrous Acid with Molecular Oxygen", J. Mol. Cat. A 2003, 200, 21-29.
O. Pestovsky and A. Bakac, "Generation of a Peroxynitrato Metal Complex from Nitrogen Dioxide and Coordinated Superoxide", Inorg. Chem. 2003, 42, 1744-1750.
O. Pestovsky and A. Bakac, "Generation and Reactivity of Rhodium(IV) Complexes in Aqueous Solutions", Inorg. Chem. 2002, 41, 3975-3982.
A. Bakac, "Reactions of Superoxo and Oxo Metal Complexes with Aldehydes. Radical-Specific Pathways for Cross-Disproportionation of Superoxometal Ions and Acylperoxyl Radicals", J. Am. Chem. Soc. 2002, 124, 9136-9144.
A. Bakac, "Rapid Cross-Disproportionation Between Superoxometal Ions and Acylperoxyl Radicals", J. Am. Chem. Soc. 2002, 124, 3816-3817.
O. Pestovsky and A. Bakac, "Nitrous Acid as a Source of NO and NO2 in the Reaction with a Macrocyclic Superoxorhodium(III) Complex", Inorg. Chem. 2002, 41, 901-905.
A. Bakac, "Kinetics of the Reaction of NO2 with a Macrocyclic Nickel Complex", Int. J. Chem. Kin. 2002, 34, 278-281.
A. Nemes, O. Pestovsky, and A. Bakac, "The Reaction of a Superoxochromium(III) Ion With Nitrogen Monoxide. Kinetics and Mechanism", J. Am. Chem. Soc. 2002, 124, 421-427.
O. Pestovsky and A. Bakac, "Reaction of Nitrogen Monoxide with a Macrocyclic Superoxorhodium(III) Complex Produces an Observable Nitratorhodium Intermediate", J. Am. Chem. Soc. 2002, 124, 1698-1703.
Z. Tóth, I. Fábián and A. Bakac, "A Flash Photolytic Study of the Reaction Between Chlorine Dioxide and Dihalogen Radical Anions", Inorg. React. Mech. 2001, 3, 147-152.
V. Butkovic, A. Bakac and J. H. Espenson, "Kinetics and Mechanism of the Reaction Between Mercury(II) and a Series of Macrocyclic Organochromium Cations", Croat. Chem. Acta 2001, 735-741.
A. Bakac, "Effects of Halide Ions and Carbon Monoxide on the Reactions of Iron(III) with Alkyl Radicals", Croat. Chem. Acta 2001, 74, 633-640.
A. Bakac, "Classical Methods", in Electron Transfer in Chemistry, Volume 1: Principles, Theories, Methods, and Techniques, Balzani V., ed. Wiley-VCH 2001, pp 395-421.
A. Nemes and A. Bakac, "Disproportionation of Aquachromyl(IV) Ion by Hydrogen Abstraction from Coordinated Water", Inorg. Chem. 2001, 40, 2720-2724.
I. A. Guzei and A. Bakac, "Macrocyclic Hydroperoxocobalt(III) Complex: Photochemistry, Spectroscopy, and Crystal Structure", Inorg. Chem. 2001, 40, 2390-2393.
A. Nemes and A. Bakac, "Kinetics and Mechanism of the Oxidation of a Substituted Phenol by a Superoxochromium(III) Ion", Inorg. Chem 2001, 40, 746-749.
A. Bakac, "Photoinduced Insertion of Molecular Oxygen into Metal-Hydrogen Bonds", J. Photochem. Photobiol. A 2000, 132, 87-89.
A. Bakac, "Hydrogen Atom Abstraction by Metal-Oxo and Metal-Superoxo Complexes. Kinetics and Thermodynamics", J. Am. Chem. Soc. 2000, 122, 1092-1097.
A. Bakac and I. A. Guzei, "Hydrogen Atom and Hydride Transfer in the Reactions of Chromium(IV) and Chromium(V) Complexes with Rhodium-Hydrides. Crystal Structure of a Superoxorhodium(III) Product", Inorg. Chem. 2000, 39, 736-740.
A. Bakac, V. Butkovic, J. H. Espenson, and M. Orhanovic, "Concurrent Homolysis, b-Elimination, and Hydrolysis of Macrocyclic Alkylchromium Complexes", Inorg. Chim. Acta 2000, 300-302, 280-284.
A. Bakac and W.-D. Wang, "Generation of a Macrocyclic Cr(V) Complex and its Reactivity Toward Organic and Inorganic Reductants and DNA", Inorg. Chim. Acta 2000, 297, 27-35
O. Pestovsky, A. Bakac, and J. H. Espenson, "Kinetics and Mechanism of the Oxidation of 10-Methyl-9,10-Dihydroacridine by Chromium(VI, V, and IV): Electron vs. Hydrogen Atom vs. Hydride Transfer", J. Am. Chem. Soc. 1998, 120, 13422.
A. Bakac and W.-D. Wang, "Hydrogen Atom Abstraction by Methyl Radicals from tert-Butyl Hydroperoxide in a Modified Fenton Reaction", Inorg. React. Mech. 1998, 1, 65.
A. Bakac, "Transition Metal Ion Initiated Chain Reactions Between tert-Butyl Hydroperoxide and Rhodium Hydrides. Rapid Hydrogen Atom Abstraction from Rhodium Hydrides by Methyl Radicals", Inorg. Chem. 1998, 37, 3548.
O. Pestovsky, A. Bakac, and J. H. Espenson, "One-Electron Transfer Reactions of 10-Methyl-9,10-dihydroacridine and the Kinetic Isotope Effects for the Intervening Ionization and Protonation of a Carbon Acid", Inorg. Chem. 1998, 37, 1616.
A. Bakac, "Kinetics and Thermodynamics of Hydrogen Atom Transfer to Superoxometal Complexes", J. Am. Chem. Soc. 1997, 119, 10726.
A. Bakac and H. D. Burrows, "Uranyl Ion: A Convenient Standard for Transient Absorption-Coefficient Measurements", Appl. Spectroscopy 1997, 51, 1916 .
Y. Mao and A. Bakac, "Uranyl-Sensitized Photochemical Oxidation of Naphthalene by Molecular Oxygen. Role of Electron Transfer", J. Phys. Chem. A 1997, 101, 7929.
A. L. Feig, A. Masschelein, A. Bakac and S. J. Lippard, , "Kinetic Studies of Reactions of Dioxygen with Non-heme Diiron(II) Complexes Leading to the Formation of (µ-Oxo)diiron(III) Complexes", J. Am. Chem. Soc. 1997, 119, 334
A. Bakac and W.-D. Wang, "Biomimetic Chemistry of Chromium. Intramolecular Conversion of Hydroperoxochromium(III) to Oxochromium(V)", J. Am. Chem. Soc. 1996, 118, 10325.
A. Bakac and L. M. Thomas, "Macrocyclic Rhodium(III) Hydrides and a Monomeric Rhodium(II) Complex", Inorg. Chem. 1996, 35, 5880.
A. Bakac, V. Butkovic, J. H. Espenson, J. Lovric and M. Orhanovic, "Electron Transfer from Aliphatic Radicals to Ring-Substituted Pyridine-N-Oxides and their Cobalt-Ammine Complexes in Aqueous Solution", Inorg. Chem. 1996, 35, 5168.
Y. Mao and A. Bakac, "Photocatalytic Oxidation of Aromatic Hydrocarbons", Inorg. Chem.1996, 35, 3925.
A. Bakac, B. Assink, J. H. Espenson and W.-D. Wang, "Metal Hydroperoxides as Oxygen Atom Transfer Reagents", Inorg. Chem. 1996, 35, 788.
A. Bakac, T.-J. Won and J. H. Espenson, "Novel Pathways in the Reactions of Superoxometal Complexes", Inorg. Chem. 1996, 35, 2171.
Y. Mao and A. Bakac, "Photocatalytic Oxidation of Toluene to Benzaldehyde by Molecular Oxygen", J. Phys. Chem. 1996, 100, 4219.
A. Bakac, W.-D. Wang and J. H. Espenson, "Uranium(VI)-Catalyzed Photooxidation of Hydrocarbons with Molecular Oxygen", Inorg. Chem. 1995, 34, 6034.
W.-D. Wang, A. Bakac and J. H. Espenson, "Oxidation and Reduction Reactions of Hydroperoxocobalt Macrocycles", Inorg. Chem. 1995, 34, 4049.
A. Bakac, "Mechanistic and Kinetic Aspects of Transition-Metal Oxygen Chemistry", Prog. Inorg. Chem., 1995, 43, 267.
A. Bakac, S. L. Scott, J. H. Espenson and K. R. Rodgers, "Interaction of Cr(II) Complexes with Molecular Oxygen. Spectroscopic and Kinetic Evidence for h1-Superoxo Complex Formation", J. Am. Chem. Soc. 1995, 117, 6483
A. Bakac and J. H. Espenson, "Autoxidation of Uranium(V). Catalysis and Inhibition by Copper Ions", Inorg. Chem. 1995, 34, 1730
J. Balla, J. H. Espenson and A. Bakac, "Kinetically Designed Conditions for the Catalytic Formation of Disfavored Products: The Reaction of (h-C5H5)Mo(CO)3• with N,N,N',N'-Tetramethyl-1,4-phenylenediamine", J. Phys. Chem. 1995, 99, 3598
J. H. Espenson, A. Bakac and J. Janni, "The Impact of Chromium Coordination on the Single-Electron Potentials for the Reduction of Oxygen to Water", J. Am. Chem. Soc. 1994, 116, 3436.
J. Balla, J. H. Espenson and A. Bakac, "Catalysis to the Disfavored Product: The Case of (h5-C5H5)Mo(CO)3•", Organometallics 1994, 13, 1073.
A. Al-Ajlouni, A. Bakac and J. H. Espenson, "Hydride Abstraction from 1,2-Diols by the Pentaaquachromium(IV) Ion", Inorg. Chem. 1994, 33, 1011.
A. Bakac, J. H. Espenson and J. A. Janni, "Oxidative Homolysis of the Superoxopentaaquachromium(III) Ion", J. Chem. Soc., Chem. Commun. 1994, 315.
A. Bakac, V. , J. H. Espenson and M. Orhanovic, "Kinetics of the Reduction of Alkyl Halides by a Chromium(II) Macrocycle", Inorg. Chem. 1993, 32, 5886.
M. Zhang, R. van Eldik, J. H. Espenson and A. Bakac, "Volume Profiles for the Reversible Binding of Dioxygen to Cobalt(II) Complexes. Evidence for a Substitution-Controlled Process", Inorg. Chem. 1994, 33, 130.
A. Bakac, "Radical Kinetics as a Mechanistic and Analytical Tool", Croatica Chemica Acta 1993, 66, 435.
A. Al-Ajlouni, A. Bakac and J. H. Espenson, "Kinetics and Mechanism of the Oxidation of Phenols by the Oxochromium(IV) Ion", Inorg. Chem. 1993, 32, 5792.
W.-D. Wang, A. Bakac and J. H. Espenson, "Kinetics and Mechanisms of the Redox Reactions of the Hydroperoxochromium(III) Ion", Inorg. Chem. 1993, 32, 5034.
A. Bakac and J. H. Espenson, "Electron Transfer and Energy Transfer Quenching of Excited States Chromium(III) Cyclam Complexes and Redox Reactions of the Chromium(II) Product", J. Phys. Chem. 1993, 97, 12249.
W.-J. Chen, J. H. Espenson and A. Bakac, "Kinetics and Mechanism of the Reaction of Chloroplatinum(II) Complexes with Alkyl Radicals", J. Chinese Chem. Soc. 1993, 40, 329
P. Huston, J. H. Espenson and A. Bakac, "Methyltrioxorhenium Catalyzes the Oxidation of a Thiolatocobalt(III) Complex by Hydrogen Peroxide", Inorg. Chem. 1993, 32, 4517
A. Bakac and J. H. Espenson, "Chromium Complexes Derived from Molecular Oxygen", Accts. of Chem. Res. 1993, 26, 519.
K. M. Christensen, A. Bakac and J. H. Espenson, "Quenching of the Excited State of Hydrated Europium(III) Ions by Electron Transfer", Chem. Phys. 1993, 176, 359.
A. M. Al-Ajlouni, J. H. Espenson and A. Bakac, "Hydrogen Peroxide Reacts with Oxochromium(IV) Ion by Hydride Transfer", Inorg. Chem. 1993, 32, 3162.
Q. Yao, A. Bakac and J. H. Espenson, "Dissociation and Recombination Dynamics of Complexes [(h5-C5R5)Cr(CO)3]2 (R = H, Me)", Organometallics 1993, 12, 2010.
S. L. Scott, W.-J. Chen, A. Bakac and J. H. Espenson, "Spectroscopic Parameters, Electrode Potentials, Acid Ionization Constants, and Electron Exchange Rates of the 2,2'-Azinobis(3-ethylbenzothioazoline-6-sulphonate) or ABTS Radicals and Ions", J. Phys. Chem. 1993, 97, 6710.
A. Marchaj, A. Bakac and J. H. Espenson, "Iron(II)-Catalyzed Autoxidation of a Macrocyclic Cobalt(II) Complex", Inorg. Chem. 1993, 32, 2399.
W.-D. Wang, J. H. Espenson and A. Bakac, "A Fenton Mechanism and an Oxochromium(IV) Intermediate in Reactions of Hydroperoxochromium(III) Ion", Inorg. Chem. 1993, 32, 2005
S. L. Scott, A. Bakac and J. H. Espenson, "Photochemical Generation of [Rh(dmgH)2PPh3)2 from [CpW(CO)3]2 and XRh(dmgH)2PPh3 (X is Cl, Br) Via 17-Electron Tungsten and Rhodium Radicals", Organometallics 1993, 12, 1044
Q. Yao, A. Bakac and J. H. Espenson, "Oxidation of a Macrocyclic Nickel(II) Complex by Alkyl Hydroperoxides", Inorg. Chem. 1993, 32, 1488
A. Marchaj, A. Bakac and J. H. Espenson, "Sixth-Order Kinetics in a Catalyzed Autoxidation of a Macrocyclic Cobalt(II) Complex", Inorg. Chem. 1992, 31, 4860.
A. Bakac, J. H. Espenson and V. G. Young, Jr., "Kinetics of Acetyl Radical Formation from Methyl Radicals and Carbon Monoxide and Crystal Structures of Two Acetylcobalt Complexes", Inorg. Chem. 1992, 31, 4959.
P. Huston, J. H. Espenson and A. Bakac, "Reactions of Thiyl Radicals with Transition Metal Complexes", J. Am. Chem. Soc. 1992, 114, 9510.
P. Huston, J. H. Espenson and A. Bakac, "b-Hydrogen Abstraction by Thiyl Radicals", Organometallics 1992, 11, 3165.
A. Marchaj, A. Bakac and J. H. Espenson, "Effect of pH on the Kinetics and Thermodynamics of Oxygen Coordination to a Macrocyclic Cobalt(II) Complex", Inorg. Chem. 1992, 31, 4164.
S. L. Scott, A. Bakac and J. H. Espenson, "Preparation and Reactivity of a Cationic Dichromium-Semiquinone Complex", J. Am. Chem. Soc. 1992, 114, 4605.
S. L. Scott, A. Bakac and J. H. Espenson, "Oxidation of Alcohols, Aldehydes and Carboxylates by the Aquachromium(IV) Ion", J. Am. Chem. Soc. 1992, 114, 4205.
A. Bakac and J. H. Espenson, "A High-Yield One-Step Synthesis of trans-[Cr([14]aneN4)Cl2]Cl and its Conversion to trans-[Cr([14]aneN4)(H2O)2](CF3SO3)3", Inorg. Chem. 1992, 31, 1108.
