个人简介

Education: B.A., 1982, Reed College; Ph.D., 1988, Harvard University Awards: NSF Postdoctoral Fellow, 1988-91, University of California at Berkeley. Shell Foundation New Faculty Award 1993-95, Bing Teaching Award 1995-98, Hoefer Teaching Award 1997 , Dinkelspiel Award for Distinguished Teaching Contributions at Stanford, 2003

研究领域

Inorganic/Organic

Our research interests are in area of synthetic inorganic and organic chemistry and are focused on creating new, discrete catalysts. Much of our inspiration derives from metalloenzymes that are capable not only of remarkable regio- and stereospecific organic transformations but also highly energy efficient transformations such the reduction of dioxygen to water. The metalloenzyme structures and electronic spectroscopy provide critical insights into the intimate metal ligation that might be necessary to construct small functional synthetic metal complexes. Extending the chemistry beyond the constraints of a protein matrix is our ultimate goal. For these redox active metal sites, the ligation environment is coupled tightly to the functional chemistry. Yet, focusing solely on the intimate metal ligation is not generally sufficient to create an efficient catalyst. Site-isolation of the active oxidant may also be necessary. This can be achieved synthetically either by supporting the metal complex on a solid matrix or by appropriate design of the ligand periphery. Movement of these complexes into silica based materials or onto electroactive electrodes represents a new direction for the group in the development of these bio-inspired metal-based catalysts. Of all the available metals, biological systems primarily use copper or iron sites to activate dioxygen for oxidative transformations. In our lab, we have focused on functional models of several enzymes including galactose oxidase (Cu), tyrosinase (Cu), lipoxygenase (Fe, Mn), and several mononuclear non-heme enzymes that require alpha-ketoacids as co-reductants (Fe). Extensive spectroscopic and kinetic investigations, often at low temperatures, coupled to extensive DFT calculations provide keen insights into these complexes and their transiently stable oxidized forms. Such studies have resulted in faithful tyrosinase functional models, self-assembled to the active oxidant core from simple monodentate imidazole ligands at extreme solution temperatures (-125° C), along with temporally and operationally efficient epoxidation and C-H hydroxylation catalysts, capable of oxidizing a wide range of electron deficient olefins and strong C-H group at exceedingly fast rates.

近期论文

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Primary Amine Stabilization of a Dicopper(III) Bis(µ-oxo) Species: Modeling the Ligation in pMMO . Citek, C; Lin, B; Phelps, T.E.; Wasinger, E.C.; Stack, T.D.P. J. Am. Chem. Soc. 2014, 136, 14405-14408. DOI: 10.1021/ja508630d Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer . Thomas, A.M.; Lin, B; Wasinger, E.C.; Stack, T.D.P. J. Am. Chem. Soc. 2013, 135, 18912-18919. DOI: 10.1021/ja409603m Squish and CuAAC: Additive-Free Covalent Mono layers of Discrete Molecules in Seconds . Pellow, M.A.; Stack, T.D.P.; Chidsey, C.E.D. Langmuir 2013, 29, 5383-5387. DOI: 10.1021/la400172w Catalytic Phenol Hydroxylation with Dioxygen: Extension of the Tyrosinase Mechanism beyond the Protein Matrix . Hoffmann, A; Citek, C.T.; Binder, S; Goos, A; Rubhausen, M; Troeppner, O; Ivanovic-Burmazovic, I; Wasinger, E.C.; Stack, T.D.P.; Herres-Pawlis, S. Angew. Chem. Int. Ed. 2013, 52, 5398-5401. DOI: 10.1002/anie.201301249 Gas-Phase Azide Functionalization of Carbon . Stenehjem, E.D.; Ziatdinov, V.R.; Stack, T.D.P.; Chidsey, C.E.D. J. Am. Chem. Soc. 2013, 135, 1110-1116. DOI: 10.1021/ja310410d Recent advances in phenoxyl radical complexes of salen-type ligands as mixed-valent galactose oxidase models . Lyons, C.T.; Stack, T.D.P. Coord. Chem. Rev. 2013, 257, 528-540. DOI: 10.1016/j.ccr.2012.06.003 Electrochemical and spectroscopic effects of mixed substituents in bis(phenolate)-copper(II) galactose oxidase model complexes . Pratt, R.C.; Lyons, C.T.; Wasinger, E.C.; Stack, T.D.P. J. Am. Chem. Soc. 2012, 134, 7367-7377. DOI: 10.1021/ja211247f Self-assembly of the oxy-tyrosinase core and the fundamental components of phenolic hydroxylation. Citek, C; Lyons, C.T.; Wasinger, E.C.; Stack, T.D.P. Nat. Chem. 2012, 4, 317-322. DOI: 10.1038/nchem.1284 Discrete Complexes Immobilized onto Click-SBA-15 Silica: Controllable Loadings and the Impact of Surface Coverage on Catalysis. Nakazawa, J; Smith, B.J.; Stack, T.D.P. J. Am. Chem. Soc. 2012, 134, 2750-2759. DOI: 10.1021/ja210400u Sulfanyl Stabilization of Copper-Bonded Phenoxyls in Model Complexes and Galactose Oxidase . Verma, P; Pratt, R.C.; Storr, T; Wasinger, E.C.; Stack, T.D.P. PNAS 2011, 108, 18600-18605. DOI: 10.1073/pnas.1109931108 Structural Dynamics of a Catalytic Monolayer Probed by Ultrafast 2D IR Vibrational Echoes . Rosenfeld, D.E.; Gengeliczki, Z.; Smith, B.J.; Stack, T.D.P.; Fayer, M.D. Science 2011, 334, 634-639. DOI: 10.1126/science.1211350 Deposition of dense siloxane monolayers from water and trimethoxyorganosilane vapor . Lowe, R.; Pellow, M.; Stack, T.D.P.; Chidsey, C.E.D. Langmuir 2011, 27, 9928-9935. DOI: 10.1021/la201333y Tale of a Twist: Magnetic and Optical Switching in Copper(II) Semiquinone Complexes . Verma, P; Weir, John; Mirica, L; Stack, T.D.P. Inorg. Chem. 2011, ASAP. DOI: 10.1021/ic200958g Electrocatalytic O2 Reduction by Covalently Immobilized Mononuclear Copper(I) Complexes: Evidence for a Binuclear Cu2O2 Intermediate . McCrory, CCL; Devadoss, A; Ottenwaelder, X; Lowe, RD; Stack, T.D.P.; Chidsey, C.E.D. J. Am. Chem. Soc. 2011, 133, 3696-3699. DOI: 10.1021/ja106338h Bis(µ-oxo) Dicopper(III) Species of the Simplest Peralkylated Diamine: Enhanced Reactivity toward Exogenous Substrates . Kang P, Bobyr E, Dustman J, Hodgson KO, Hedman B, Solomon EI, Stack T.D.P. Inorg. Chem. 2010, 49, 11030-11038. DOI: 10.1021/ic101515g Unexpected C-carbene-X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions . Lin BL, Kang P, Stack T.D.P. Organometallics 2010, 29, 3683-3685. DOI: 10.1021/om1005726 Facile C-H Bond Cleavage via a Proton-Coupled Electron Transfer Involving a C-H center dot center dot center dot Cu-II Interaction . Ribas X, Calle C, Poater A, Casitas A, Gomez L, Xifra R, Parella T, Benet-Buchholz J, Schweiger A, Mitrikas G , Sola M, Llobet A, Stack T.D.P. J. Am. Chem. Soc. 2010, 132, 12299-12306. DOI: 10.1021/ja101599e Ligand Radical Localization in a Nonsymmetric One-Electron Oxidized Ni-II Bis-phenoxide Complex . Storr T, Verma P, Shimazaki Y, Wasinger E. C., Stack T.D.P. Chem. A Eur. J. 2010, 16, 8980-8983. DOI: 10.1002/chem.201001401 Detailed Evaluation of the Geometric and Electronic Structures of One-Electron Oxidized Group 10 (Ni, Pd, and Pt) Metal(II)-(Disalicylidene)diamine Complexes. . Shimazaki, Y.; Stack, T. D. P.; Storr, T. Inorg. Chem. 2009, 48, 8383-8392. DOI: 10.1021/ic901003q Reaction Coordinate of a Functional Model of Tyrosinase: Spectroscopic and Computational Characterization. . Holt, B. T. O.; Vance, M. A.; Mirica, L. M.; Heppner, D. E.; Stack, T. D. P.; Solomon, E. I. J. Am. Chem. Soc. 2009, 131, 6421-6438. DOI: 10.1021/ja807898h