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  • Charles G. Riordan, Vice President for Research, Scholarship and Innovation

    Vice President for Research, Scholarship and Innovation
    Professor
    University of Delaware
    124 Hullihen Hall
    Newark, DE 19716
    (302) 831-1073
    http://www.udel.edu/chem/riordan/

    Biography

    (b. 1964) B.A., 1986, College of the Holy Cross; Ph.D., 1990, Texas A&M University; Research Associate, 1990 – 1992, University of Chicago

    Current Research

    The Riordan laboratory focuses on frontier synthetic and mechanistic problems in bioinorganic and coordination chemistry that may be probed through chemical synthesis, reactivity and kinetic studies. This bioinspired approach requires the tools of both synthetic and physical inorganic chemistry. Specifically, we are interested in using low valent nickel complexes to activate small molecules, in particular dioxygen, so as to understand the pathways of dioxygen activation and utilization as an abundant and environmentally responsible oxidant. In intellectually related pursuits, the oxidation of metal hydroxide complexes as a strategy to investigate homogenous water oxidation is another area of current interest. Objectives include deducing the geometric and electronic structures of new molecules, in particular reactive intermediates, via application of a wide range of contemporary physical methods and correlating structure with chemical reactivity.

    Students in the laboratory are trained in the areas of synthesis, including anaerobic techniques, spectroscopy, reaction kinetics and mechanism. Recent Riordan group alumni are employed in industry, academia and government laboratories.

    DIOXYGEN ACTIVATION O2 is the ideal oxidant for a wide range of homogeneous catalytic processes. We have discovered that a series of readily accessible nickel(I) complexes react avidly with O2, reducing the O=O bond to varying degrees, generating metastable intermediates,Figure 1. The geometric and electronic structures and reactivity of these new complexes are of current interest. A surprising observation is that the sulfur-containing ancillary ligands are not oxidized during the reaction.

    SULFUR AND SELENIUM ACTIVATION In expanding the bioinspired approach of Oactivation by nickel(I) complexes, activation of the heavier congeners, sulfur and selenium, has led to the isolation of a wide range of new chemical entities with interesting electronic and geometric structures, in which the nature of the sulfur or selenium bridging ligand is determined by the identity of the supporting ligand AND the metal-to-chalcogen stoichiometry. A sampling of recently deduced structures is provided in Figure 2.

    Representative Publications

    • C. G. Riordan "Coordination Chemistry of Poly(thioether)borate Ligands," Coord. Chem. Rev.254DOI: 10.1016/j.ccr.2010.01.007
    • K. M. Van Heuvelen, J. Cho, T. Dingee, C. G. Riordan and T. C. Brunold "Spectroscopic and Computational Studies of a Series of High-Spin Ni(II) Thiolate Complexes," Inorg. Chem.49DOI: 10.1021/ic100362q
    • K. M. Van Heuvelen, M. T. Kieber-Emmons, C. G. Riordan and T. C. Brunold "Spectroscopic and Computational Studies of a Trans-µ-1,2-Disulfido-Bridged Dinickel Species, [{(tmc)Ni}2(S2)](OTf)2: Comparison of End-on Disulfido and Peroxo Bonding in (Ni2+)2 and (Cu2+)2 Species," Inorg. Chem.49DOI: 10.1021/ic901733h
    • M. T. Kieber-Emmons, K. M. Van Heuvelen, T. C. Brunold and C. G. Riordan "Synthesis and Spectroscopic Identification of a µ-1,2-Disulfidodinickel Complex," J. Am. Chem. Soc.131DOI: 10.1021/ja807735a
    • M. T. Mock, C. V. Popescu, G. P. A. Yap, W. G. Dougherty and Charles G. Riordan "Monovalent Iron in a Sulfur-Rich Environment," Inorg. Chem.47DOI: 10.1021/ic7023378
    • M. T. Kieber-Emmons and C. G. Riordan "Dioxygen Activation at Monovalent Nickel," Acc. Chem. Res.40DOI: 10.1021/ar700043n

 

 

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  • Chemistry and Biochemistry
  • 102 Brown Laboratory
  • University of Delaware
  • Newark, DE 19716, USA
  • Phone: 302-831-1247
  • chemistry@udel.edu